•J-_-7ngo:dp,:::i:sn

OVERVIEW
I. Coordination compounds: Compounds in which the central i. Bidentate ligands:
atom is linked to a number of ions or neutral molecules tt
called ligands by coordinate bonds i.e., by donation of lone Ethylenediamine(e7e) H2N(CH2)2NH2 and
pair of electrons by ligands to the central metal atom are
called coordination compounds. oxalateion(oX2-)i:::>
2. Double salts, mixed salts and complex compounds: Both
double salts and complexes are formed by the combination ii. Tridentate or terdentate ligands:
of two or more stable compounds in stoichiometric ratio. Diethylenetriamine (diene):
Hence, they are additional molecular compounds.
ii ii i]
However, double salts dissociate into simple substances
H2fitcH2j2rfutcH2)2rd.H2
or ions completely when dissolved in water, whereas in
complex compounds, the complex ion almost does not iii. Tetradentate ligand:
dissociate. For example, Triethylene tetraamine (triene):
a. Kcl.Mgc12.6H20 -K© + Mg2+ + 3Cl©+ 6H20
ii hi fi fi
Camallite (double salt)
H2rftcH2>2rfHtcH2j2NHtcH2>2riil2
b. Bleaching powder Caoc12 is a mixed salt. It is a
salt of Ca2+ [Link] the anions present are Cl® and iv. Pentadentate ligand:
C10°¢ypochloriteion).Similarly,NaKS04isamixed Tetraethylenepentaamine(tetraene):
salt in which there are two cations Na© and K© ions and ttttt
one anion S042- NH2tcH2j2riHtcH2)2itHtcH2j2NHtcH2j2iirl2
c. K4[Fe(CN)6] 4K® + [Fe(CN)6]4-
V. Hexadentate ligand:
Potassium ferrocyanide (Complex compound)
Ethylene diaminetetraacetato ion:
3. Ligands and central metal atom/ion: The donor atoms,
molecules or anions which donate a pair of electrons to the t
metal atom or ion and form a coordinate bond with it are
called ligands. The metal atom or ion to which these ligands <go°oC:==::7(CH2)2-£<:=:=:;:}
are attached is called central metal atom br ion.
4. Denticity: The number of coordinating or ligating groups 6. Ambidentate ligands : Unidentate ligands containing more
present in a ligands is called the denticity of that ligand. than one coordinating ato_ms are called ambidentate ligands.
5. Tines of ligands: Ligands can be of the following types e.g., No2° (O=Y--0° and o=N_o°:+
depending on the denticity of the ligand.
a. Monodentate or unidentate ]igand: They have one ovitrito-N) ovitrito -O)
donor atom, i.e. they donate only one lone pair of ©©
scN©( NCS:+ and SCN:+
electronstothecentralatome.g.,Xe,H26:,NH3,:CO,
(thiocyanato) (i sothiocyanato)
SCNe etc.
b. Polydentate or multidentate ligands: These ligands 7. Flexidentate ligands: Ligands which have more than one
coordinate using two or more donor atoms. Name and donorsite,likeS042-,C032~[Link]
structures of some of them are shown below: monodentate ligand in one complex and bidentate [Link]
complexes are known as flexidentate ligands.
EDTA generally acts as a hexadentate ligand but it can also
act as a pentadentate and tetradentate ligand.
7.2 Inorganic chemistry

8. Coordination number (CN): It is defined as the number of

coordinate bonds formed with the central atom/ion by the
ligands, e.g. H2N: :iH;H
\5i/-`\CH2
[Cr(N113)2C12(H20)2]e, CN = 2 + 2 + 2 = 6
Coordination number in case of polydentate ligands attached ©Br/ H\N-CH2 I

to central metal atom/ion is equal to number of polydentate

ligand multiplied by their denticity, e.g., Chelating ligands form more stable complexes than
monodentate analogous.
i. [Cr(e#)2(H20)2]3+;CN=2 X2+2=6
14. Homoleptic, heteroleptic and labile complexes:
ii. [Cr(edta)]e; CN = 1 x 6 = 6 Complex in which the metal atom/ion is linked to only
9. Coordination number (CN) of some central metal atom/
ion. (Refer to Table 7.6). i::(E:3)o6i3`!?a#:[Link]:;`l`eexde:oi:o#:Lc,choem:lee,::s;,e..£
10. Coordination sphere or coordination entity and counter ion is linked to more than one kind of ligands are called
ion: The central atom and the ligands which are directly heteroleptic complexes, e.g., [Cr(NH3)2(H20)2Br2]©.
attached to it are enclosed in square brackets and are Thecomplexinwhichligandcaneasilybereplacedbyother
collectively termed as coordination sphere or coordination ligands is called labile complex.
entity. 15. Homonuclear and poLynuclear complexes: Complexes
The ionisable groups outside the square brackets are called
counter ions, as shown in the compounds. ino:ohi:t[:anr[¥o°mn;[e¥:::[e.:t.;rcr£(SH:roe)S6e]gi.a::m%]°e¥s::
which more than one metal atom/ion is present are known
[CrovH3)5Cl]S04 - [Cr OJH3)5Cl]2+ + S042-
ccordinatiTri compound cen*i ¥ -_J
Counter
aspo[ynuc]earcomp]exes,e.g.,[te„,2Cr<8E>crten,2]

metal ion 16. Nomenclature and formula writing of coordination

lion t compounds: Refer to Section 7.5.
Coord##here 17. a. Werner's coordination theory: Refer to Section 7.6.
b. ¥ecr:::;:x#:: :;:t£:x°)nm:fmc:#::eoxfe: :=F€rNe:;::i:
11. Coordination polyhedron: The spatial arrangement of
the ligand atoms which are directly attached to the central which is equal to 6.
metal atom/ion in a definite direction thereby giving a The minimum value of x = CN -O.S. = 3
definite geometry to the complex compound/ion is called
coordination polyhedron around the central metal atom/ Werner's coordination compounds
ion. The various polyhedra are tetrahedral, square planar,
Werner Modern lonisatton prirmary J Secon any
octahedral, square pyramidal, trigonal bipyramidal,
complex notation valehcy + + va,ency
pentagonal bipyramidal etc. and satisfied + + satisfied +
12. Oxidation number (ON) ol. central atom: It is defined colour byloN) a by`€M
as the charge that central metal ion would cany if all the
• ligands are removed along with electron pairs. Fcjr example, (A) CoC13.6NH3 [Co [Co 3Cl© 6NH3
Yellow OJH3)6]C13 orH3)6]3++3Cl©
[CrBrc10VH3)2(H20)2]C;104] -

[C:Br-]Cl-]0{Hg)2(H20)2]©+Clog 3Cl© 5NH3

(8) CoC13.5NH3 [CoC1 [CoC1
Charge on complex ion = +I Purple 0{H3)5]C12 O{H3,5]2++2Cl© one cl©
Let charge on Cr = I ;nnceLucdi88withbothvalencies)
Total charge of ligands = -1 ~ 1 + 0 + 0 = -2
... JX:-2-+l ...x-3
(C) CoC13.4NH3 [COC12 3C1© 4NH3
Hence oxidation number of Cr = +3 or (Ill).
Exists in 2 OrH3)4] #i;:]® 2Cl©
Note: The central atom in a complex compound /ion can isomers cz.s Cl +clo incc:8d*[gh
be even a nor-metal, e.g„ in Ba[BrF4]2, central atom in & givcr#s with both va-
complex ion is Br. green andvioletincolour lencies)
13. Chelation: When coordination of two or more donor atoms
from a polydentate ligand to a single central atom/ion takes
place forming a closed or cyclic ring structure, it is called 3Cl© 3NH3
(D) CoC13.3NH3 [COC13 [COC13
chelation and the ligand is called a chelating ligand. The all withbothva-lenciesorwithdualnature. 3C1©
0¢H3)3] quH3)3]
close ring compound thus formed is called chelate (or metal
chelate). [Chelos, Greek word means `crab']. For example,
Tridentate chelation in [PtBr(dien)]©
 Coordination compounds 7.3

Note: Conductance of the above complex will be in the order of has two isomeric forms having red and yellow
A=8=C=D. colours. The red colour isomer is [Co(NH3)5(ONO)]2+

c. Failure of Werner's coordiation theory: Refer to (having Co + 0 linkage) while the yellow isomer is
Section 7.6.2. [Co0VH3)50V02)]2+ (having Co + N linkage).
18. Sidgwick theory and effective atomic number (EAN): iv. Coordination isomerism: Coordination compounds
In. order to explain the stability of complexes Sidgwick made up of cationic and anionic coordination entities,
proposed EAN rule. He suggested that a metal ion will show this type of isomerism due to interchange of
continue accepting electron pairs till the total number of ligands between the cation and anion entities. For
• electrons in the metal ion (after gaining one lone pair of example'
electrons from the ligands) becomes equal to that of next [CrovH3)6] [Co(CN)6] and [C00VH3)6] [Cr(CN)6]
higher noble gas. This total number of electrons is called
v. Po]ymerisation isomerism: This type of isomerism
EAN of the metal.
exists among complexes which have same empirical
EAN = (Atomic number -OS) + (CN x 2)
formula but each of the isomer is some multiple of the
For example, empirical formula, e.g.
i. EANin [Fe2+(CN)6]4-=(26-2)+(6 X 2)= 36
[PtovH3)2C12]O [Pt(NH3)4] [Ptc14] and
= Z of Kr (36) (next nearest inert gas).
[PtovH3)3Cl].2 [Ptc[4]
ii. EAN in [Fe3+(CN)6]3-= (26 ~ 3).+ (6 x 2) = 35
These isomers are distinguished by mass spectroscopic
I Z of Kr (36) (next nearest inert gas).
methods.
EAN rule is not valid in this case.
vi. Coordination position isomerism: This type of
19. Isomerism: Isomers are compounds having same molecular
isomerism is shown in polynuclear complexes due to
formula but different structures. The following types
interchange of ligands between the coordination spheres
isomerism are:
of various central metal ion, e.g.,

[OVH3)4Cr<gE2>CroJH3)2Br2]2+and

[BrovH3)3Cr<gE2>Cron3)3Br]2+
vii. [Link]: This type of isomerism is due to
differences in arrangement of ligands in space around
a given metal atom/ion. It is of the following two types:
A. Geometrical isomers (GI):
cis-trams isomerism: This type of isomerism occurs in
complexes having coordination number (CN) 4 (square
20. Structural isomerism: planar) and 6 (octahedral) complexes.
i. Ionisation isomerism: This type of isomerism exists a. Complexes with general formula Ma4, Mab3 and
when a counter ion in a coordination compound is itself Ma3b (square planar geometry with CN = 4) and
a potential ligand. For example, Ma6 and Ma5b or Mab5 (octahedral geometry with
a. [Crov03)(NH3)5]S04 and [Cr(S04)0+H3)5] OV03) CN = 6) do not show GI.
+3 -2 0 +3-I-I 0 b. Complexes with general formula Ma2b2 (where both
b. [CoC120VH3)4]Br and [COBrcl(N113)4]Cl `o' and `b' are monodentate) shows 2 isomers (c!.a
ii. Hydrate or solvent isomerism: It occurs when water and frcz#s), e.g., [Pt(NH3)2C12]
foms a part of the coordination entity or is outside it.
c. Ma2bc type shows 2 iosmers (cis and trams),
For example, Crc13.6H20 exists in
e.g., [Pto¢H3)2CIBr]
a. [Cr(H20)6]C13 (Violet) gives 4 ions in solution.
d. Mabcd type shows 3 geometrical isomers,
b. [Crcl(H20)5]C12.H20 ®ale green) gives 3 ions in
e.g., [PtQVH3)CI Br 1]
solution.
e. Square planar complexes having unsymmetrical
C. [Crc12(H20)4]Cl.2H20 (dark green) gives 2 ions in
bidentate ligands, show 2 GI (cz.a and /r¢#s) e.g.,
solution
[Pt(Gly)2].
d. [Crc13(H20)3].3H20 gives no ions in solution.
f. Octahedral complexes of type Ma4b2 and Ma3b3
iii. Linkage isomerism: This type of isomerism is
each exhibit 2 G.I. respectively. In case of Ma4b2 it
is classified as cz.a and /J'a#s and in case of Ma3b3, it
::Sbs::::::t::rg:::r]:inea£°on28::rp§:n#::n6arfe£.n#:
is classified as facial (fac-) and meridional (mer-).
type of isomersim arises due to different metal-ligand
(M + L) linkage. For example, [Co(NH3)5N02]2+ 9. Octahedral complexes of type Mabcdef can have 15
geometrical isomers.
7.4 Inorganic chemistry

h. Geometrical isomers do not occur in tetrahedral cz.s form is optically active but the Jr¢73s form is
complexes (CN = 4) because the relative position of optically inactive.
the ligands attached to the central metal atom/ion is
same w.r.t. each other.
8. Optical isomerism:
a. The coordination compounds having same
molecular formula but differing in their ability
to. rotate directions of the plane of polarised light
are said to exhibit optical isomerism and such
molecules are called optical isomers (enantiomers cz.s-d-foml Mirror cz.s-/-form
or enantiomorphs). iv. [M(AA)a2b2]"±, e.g., [Crc12(e#)Q¢H3)2]®
b. General formulae of optically active complexes
(one cz.f and one frcz#s)
i. [M(AA)3]"±, [M(AA)2a2]"±, [M(AA)2ab]"±, cz.s form is optically active but Jr¢7zs form is optically
[M(AA)a2b2]"±) inactive.

(where AA are symmetrical bidentate ligands)

ii. [Ma2b2C2]"±, [Mabcdef]"±, [M(AB)3f

(where AB are unsymmetrical ligands)

C. Some examples:
i. [M(AA)3]"±, e.g.„ [Cr(en)3]3+ (3 stereoisomers)

CI Cl
cz.a-d-isomer M or cis-l-tom

V. [Ma2b2C2]n±, e.g., [Pttoy)2(NH3)2C12]2+

(one cis and one trcz#s)

cz.s form is optically active but /rtz#s form is optically
inactive.
d-form Mirror /-form
Py

NH3
`Meso' or optically cz.s.-d-foml Mirror c!.s-/-foml
inactive fom (if exists)
vi. [Mabcdefl"±, e.g., [Pt(py)NH3N02CIBrl] shows
ii. [M(AA)2a2]"±, e.g., [CO(en)2C12]® 15 geometrical isomers. Each of them is optically
cz.s form = 3, (each showing optical isomerism) active. Only 3 isomers have been prepared but no
fr¢7€s form = 1 (does not show optical isomerism) form has been resolved.

©'
I

I
I

I
I
cz.s-d-fomi Mirror cz.s-/-fomi
d-isomer rm /-isomer
iii. [M(AA)2ab]n±, e.g., [Co(e#)20VH3)C1]2+
vii. [M(AB)3], e.g., [CrGJ/J')3]
(3 stereoisomers)
2 cz.a and 2 /r¢#£ forms.
(one cz.s and one fr¢#s)
Both the forms are optically active.
 Coordination compounds 7.5

b. OHO lies below H20 andNH3 in spectrochemical series,

but it produces a greater splitting.
These above weakness of CFT are explained by LFT
(Ligand field theory)
26. Stability of coordination compounds: (Refer to
Section 7.14)
27. Organometallic compound (OMC): They contain at least
I
one M{ bond. [Ni(CO)4] is taken as OMC although CO is
cis or trans-d-isomer cis of trans-I-isomer
not organic compound. Metal cyanides (e.g. KCN) are not
[Link] [Ma4b2]"± and [Ma3b3]"± types Show two included in OMC, although they contain M{ bond.
geometrical isomers (cz.a and trcz#S) or fac- and mer-). A. OMC are of two types:
But none of them are optically active.
i. s-and p-block OMC or a complexes
ir.3g[Link],c,::(:i::,:8::::ai:i:i:aF:;.ai::tsa:: ii. d- and f-block OMC or 7[-complexes.

i.e., d- and /-form. s-and p-block OMC: The bonds in aHryls of s-block
elements are highly polar.
21. Bonding in coordination compounds: To explain the
definite geometry, magnetic and optical properties of In the OMC of group 14,15 and 16, M{ bonds are of
coordination compounds, various theories were put forward, relative lower polarity.
e.g., Methyl compounds of Li, Na, Be, Mg and Al
i. Valence bondtheory (VBT) in l930s are associated with alkyl bridges and multicentre
2 electron bond. e.g., Li4(CH3)4, A12(CH3)6.
ii. Crystal field theory (CFT) in 1950s and 1960s
8. d- and f-block O.M.C.
iii. Ligand field theory (LFT) in 1960s onwards
i. Zeise's salt: [Ptc13(C2H4)]° or K[Ptc13(n2-C2H4)]
iv. Molecular orbital theory (MOT) in 1960s onwards
ii. [Ni(CO)4], [Cr(CO)6], C02(CO)8, [Fe2(CO)9]9
But only first two theories are discussed in this chapter.
[Mn2(CO),o], Fe(CO)5, Fe3(CO)12.
22. a. Valence bond theory (VBT): Refer to Section 7.10
iii. Ferrocene:
b. Drawbacks ofvBT: (Refer to Section 7.10.6)
[Fe(115-C5H5)2] (bicyclopentadienyl iron(II)) and
c. Refer to Table 7.17, for geometry (shape), hybridisation
dibenzene chromium [Cr(T|6-C6H6)2]
and magnetic properties of some of the complexes.
These compounds are called METALLOCENE or
23. Crystal field theory (CFT): (Refer to Section 7.11)
sandwich compounds which have 7t-bonding of
24. Spectrochemical Series: carbocyclic rings to metal atoms.
Some ligands have been arranged below from the weakest They are highly specific for homogeneous catalysis
to the strongest. This arrangement is` called spectrochemical process like carbonylation, hydrogenation and
series as shown below: polymerisation.
|©<Br©<S2-<SCN©<C1°<F®<N03°<8H<urea<EtoH 28. a. Metal carbonyls: Homoleptic carbonyls (compounds
containing CO ligands only) formed by most of TE.
Weak field ligand
Metal carbonyls are not regarded as organometallic
<C2042-(OX)<02-<H20<NCS®<EDTA<NH3
compounds (OMC) in the true sense because CO is not
Border line field ligands an organic compound. However, they are studied along
with other OMCs.
=#e3:¥#;8=e¢#e:ecdi;armine(en)<dipyridy|(dipy) b. Nature of bonding in metal varbonyls: CO, as
a ligand binds to CMA by C-atom forming weak
Strong field ligands
a-bond to the CMA, CO acts also as an acceptor ligand
A pattern of increasing a donation is: and forms a 7t-bond to the metal. This is called synergic
Halide donors < N donors < C donors bonding which stabilises the (M-L) interaction.
29. Impolfance of coordination compounds:
Note: Oxalate, generally behaves as weak field ligand but with
a. cis-platin and taxol are used in cancer (tumours) therapy.
Co (cobalt), it behaves as a strong field ligand like NH3 e.g.; in
b. Coordination compounds are of great importance to
the compound [Co(OX)3]3-.
biological system e.g.

25. Limitation of CFT: i. Chlorophylls (the green plant pigment that acts as
a. Assuming ligands as point charges, it follows that anionic a photosensitiser in the photosynthesis in plants
ligands should exert greatest splitting effect, but anionic Ligand = Polphyrin, CMA = Mg2|
ligands are found at low end of the spectrochemical ii. Haemoglobin (acts as 02 carrier, red Pigment of
series. blood) [Ligand =Porphyrin, CMA = Fe2+]
 7.6 Inorganic chemistry

iii. Myoglobin (which stores 02 and is a regulator of j. Many ligands (organic reagents) are used for the
respiration. (Ligand = Porphyrin, CMA = Fe2+) gravimetric estimation of number of metal ions.
•` ,. - r-r.,-

iv. Vitamin 8,2 or cyanocobalamine (antipemicious

'ri£`€Sinrided\:a
orgind
anaemia factor. Ligand = Corrin, CMA = Co2+) N®.:I

v. Enzyme e.g., carboxy peptidase A and carbonic 1. cu2+ Red pH Benzoin oxime
anhydrase (catalysis of biological system, CMA = - 9- 1 0 (or cupron)
zn2+)
c. Extraction ofAu andAg: The noble metals likeAu and 2. Ni2+ Red pH DMG
-9-10 (Dimethylgly-Oxime)
;,g[Link]x:::gt|,eAruo(r:#8u:[Link]:,:.of
and Au is precipitated by addition of Zn metal. 3. Fe3+ Broun - 1,10-phenth-rolinetoh)
d. Purification of metaLs 04ond's process): Impure Nickel
isconvertedto[Ni(CO)4]whichondecompositiongives 4 A13+ Blue - 8~hydroxy-quinoline
pure Ni.
e. When certain metals are present in toxic proportions in 5. co2+ Red - Ch-nitroso- p-naphihol
plant and animal system, they are removed by chelating
ligand, e.g., excess of Cu and Fe is removed by the
chelating ligands. D-Pencillamine and desferrioxime k. Test for S2-ion: The complex sodium nitroprusside,
8 via the formation of coordination compounds. Na2[Fe[[(CN)5NO®] with S2-gives violet colour.
f. Calcium dihydrogen salt of EDTA is used in treatment
as an antidote for the Pb poisoning. S2-+ [Fe[[(CN)5NO©]2--[Fe[](CN)50VOS)© ]4-
Sulphide ion Violet colour
8. %:2Tfn£: #Sge2q ;nandbe:esTe£:t£]::,;heest::radt::S;e::u¥:3i
I. Badecker reaction: This reaction is used for test of
sulphite ion.
gig:r::]Cuee£:ihce;r+¥gov#]ees;.K&ValueofMg2+complex
Na2[Fe]](CN)5NO®]+Na2S03-Na4[Fe(CN)50JOS03)]
h. Ziegler-Natta [Tic14 + (C2H5)3Al], a heterogenous
Sod, nitroprusside Sod, sulphite
catalyst (insoluble in the reaction medium) is used in
the polymerisation of alkenes at atmospheric pressure in. Everitt's salt: It is K2[Fe(CN)6], obtained by reduction
and at ambient temperature (i.e., for the preparation of of Prussian blue.
HDPE).
i. Wilkinson's homogeneous catalyst [Rhc1(Pph3)3] n. [Fer[(CN)6]4-, [Fe][[(CN)6]3- and SCN° ions are used

(soluble in the reaction medium) is used in the for the detection of various metal ions as shown below:
hydrogenation of alkene.

h?!`::,?:|;S: :;\ : '\ : v ( -S+ y< \- \ ; ;S.:a

¥es"gF r 2j¥r`,:vs.:| u&&SJi`i?y-`-`y ,(`tr
;^`r , \ Fest`` s:r<orv.'r/ ^`•{^`i;`-:-;:,>f~;J. •:v::-z\r ^ ex`Ljset ' : 2*^J.A: v^ `<`.3¥£`:{;`t

s* =tyo* ;-`(? : i i.3x--;i `;¥:;`- 2 •5,i:,,:: i ,i(.,1, -,,,ife ; -. . i(Z

Zn -,(-
- ?L Cti s7;a;;:^¥= qu ,r:~` ;iise?8i;

1. [FeL](CN)6]4- Fe2n[Fe[[(CN)6] Fe4rt][FeT((CN)6]3 Zn2[Fe[[[(CN)6] Cu2[Fe][(CN)6] -

Ferrocyanide ion Ferro~ferrocyanide(Whiteppt.) Ferri-ferrocyanideQ'russianblue) Bluish white ppt. Chocolate ppt.

2. [Fe'r[(CN)6]3~ Fe3H[Fe[n(CN)6]2 Fe['[ pre]]](CN)6] - - Co3n[Fe(CN)6]

Ferricyanide ion Ferro-fericyanide Ferri-ferricyanide Reddish broun
(Tunbull's blue) (Brown solution) colour
3. scNe - [Fe[][(SCN)3]
- - [CO]{(SCN)4]2-
Thiocyanate ion Blood red colour Blue colour

±=======:===_~_._._...I._,_.|L-I------_.---.--------------~---'f~..i__.--L4--I+LIL_-L==:==::=
 Coordination compounds 7.7

7.1 INTRODUCTION 7.2.1 TYPES OF COMPLEX

The transition elements form a large number of complex 1. Cationic complex or positively charged complex: Complex
compounds in which the metal atoms are bound to a number
of anions or neutral molecules, such compounds are called :%nudrcE:y4=i)4a]n2:Lsnoi9_u{:.3)[4¢:?#ir:)n4]Ls°6is:t:::e§L:::
coordination compounds. Chlorophyll, haemoglobin and vitamin positive charge.
8]2 are coordination compounds of Mg, Fe and Co respectively. 2. Anionic complex or negatively charged complex: Complex
Variety of metallurgical processes, industrial catalysis and K3[Fe(CN)6] gives three K© and [Fe(CN)6]3- ions on
analytical reagents involve the use of coordination compounds.
[Link][Fe(CN)6]3-inK3[Fe(CN)6]carries
These compounds also find many applications, e.g. electroplating,
net negative charge.
textile dyeing and medicinal chemistry.
3: Neutral complex has cation and anion both as complex ion:
7.2 COMPLEX ION. Complex [PtovH3)4] [Ptc14] has [PtovH3)4]2+ and [Ptc14]2-
as cationic and anionic complex ion.
It is defined as an electrically charged ion which consists of
4. Neutral complex having no net charge, e.g. [Ni(CO)4].
central metal atom/ion linked to group of molecule ions by means
of coordinate bonds.
In general, complex ion is represented as [ML„]± X where M is
7.3 SOME IMPORTANTTERMS USED
central metal ion, L is ligand bonded to M by means of coordinate IN COORDINATION COMPOUND
bond, ;c is the coordination number of metal M and x is the net
7.3.1 COORDINATION ENTITYAND COUNTER ION
charge on the complex.
The main points of difference between a double salt and a A coordination entity constitutes a central atom/ion (usually
complex compound are summarised in Table 7.1. a metal) to which are attached a fixed number of molecules/
Table 7.1 Difference between a double salt and a complex ions. It may be neutral or charged. This is also known as
compound coordinationsphereandiswritteninside[]brackets,e.g.[Ag(CN)2]e
The ions present outside the coordination sphere constitute the
s* Double ,J\ :^J:r J s- €om#,eel ::
counter ion/ionisation sphere.
No. salt No. €&mietlrlS `
The coordination entity and counter ions in the following
1. I They exist only in the 1. They exist in solid state as coordination compounds:
solid state. In aque- well as in aqueous solu-
ous solution, they tion, because the complex [Cr(N113)6]C13, K4[Fe(CN)6], K2[Ptc14], [Ni(CO)4],
i dissociate completely ion does not dissociate into K2[Ni(CN)4], 02[PtF6], Xe[PtF6] are as shown below.

i into ions. ions.

`^,''fyrfe`df`:::(y
2. They usually contain 2. The silxple salts from coordinapan natiori,.:.
•i¥(| ^`^rr\

two simple salts in wbich they are formed compdiend ' \ -f` en coordinattor` - :ianrr``

[Link]- (
equimolar propor- may or may not be in equi-
tions' mo lan proportions. [crour3)6]cl3 [CrovH3)6]3+ Positivelychargedorcationic 3Cl©
3. They are ionic com- 3. They may or may not be
pounds and do not ionic but the complex part
contain any coordi- always contains coordinate K4[Fe(CN)6] [Fe(CN)6]3- Anionic 4K©
mate bond. bonds.
4. The metal ions show 4.
their normal valency.
The metal ion satisfies
its two types of valencies
K2[Ptc14]
Ni(CO)4]
[ptcl4]2-
INi(CO)4]
Anionic
Neutral -
2K®

called primary and second- K2INi(CN)4] INi(CN,4]2- Anionic 2K®

any valencies (discussed in 02[PtF6] [pt+5F6]© Anionic 02©(Dioxygenyl)
Section 7.5).
5. They lose their idem- 5. They retain their identity Xe[PtF6] Anionic xe®
[pt+5F6]©
tity in the solution. in the solution.
6. The properties of 6. The properties of these
7.3.2 CENTRAL AroM/loN
double saits are same compounds are different
as those of their con- from its constituents. In the coordination entity, the atom/ion (usually a metal) to which
stituent compounds. one or more neutral or charged molecules are bound by means of
coordinate bond formation in a definite geometrical arrangement
3[CoquH3]6,K4FTe(CN)6][Link] around it, is called the central atom/ion.
able and almost does no ssociate into
`penetrating
ecalled`perfectcomplexe Thecentralatom/ionisalsoknownascentreofcoordination,
dslikeK2[Cd(CN)4],in ecomplex e.g. , the central atom/ion in the following compounds [Co(r`m3)6]
mt to give C13, K3[Fe(CN)6], [Ptc140JH4)2], INi(CO)4] are as shown below.
€ called `imperfect or norm plexes'.
7.8 Inorganic chemistry

• camp,ex ^^;''^::'Ssi3ofs£Q§
ass83? ' ?i;`t,L \asLi{i§ff&Y;:r
molecules or ionic. Examples of monodentate ligands are
^s+ y,,^ €eStral ian \:€: 19^:,:,RES;;ty\{
given in Table 7.2.
[CoQ{H3)6]C[3 co3+
Table 7.2 Some examples of monodentate or unidentate
K3[Fe(CN)6] Fe3+
ligands
Ptc14qu3)2] pt4+
J \,Nests
Neut ral t5ye::r . - ( ioSifroe , , ,
Nio ^fldg . ,
INi(CO)4] ligands + - Igan 8 `,I -
• ..tiga

+:NH3 Am- F© Fluo- No® Nitroso-

7.3.3 LIGANDS mine rido niun
Anymolecule/ionwhichcandonateatleastapairofelectrontothe ®H2N-NH3
H20 : + Aqua cle [Link] Hyra-zinium
central atom/ion to form a coordinate bond is known as ligand or
coordinating group. Further in a ligand, the atom which actually +:PH3 Phos- 0 Ac-
donatesthepairofelectroniscalledasdonoratomorligatingatom.
phine
IlocH3rf-o etato
Complex formation can be explained in terms of Lewis acid-
Lewis base concept. Central atom/ioh which accepts electron +:CO [Link] N3- Ni-trido
pair(s) from ligands act as Lewis acid, whereas ligands which
donate one or more pair of electron to central atom/ion acts as
+:NO Nitro-syl NH2e Ami-do
Lewis base. This also explains why transition elements having
empty d-orbitals fom coordination compounds easily,
b. Po]ydentate or multidentate ligands: When two or more
[Link] Classification of Ligands
donor atoms present in the ligand coordinates with the
Ligands can be classified on the basis of denticity, i.e. the number central ion, the ligand is known as polydentate ligand. These
of donor atoms present in the ligand molecule, which are foming may be bidentate, tridentate, tetradentate, pentadentate,
coordinate bond with the central atom/ion, as follows: hexadentate when it is coordinated with the central atom/
a. Monodentate or unidentate ligands: If the ligand ion at 2, 3, 4, 5, 6 sites respectively. In other words, one
coordinates with central atom/ion using only one donor molecule/ion of these ligands makes 2, 3, 4, 5, 6 (M +:
atom (irrespective of the number of donor atoms in it), it is L) coordinate bonds respectively. Examples of polydentate
known as monodentate ligand. These ligands may be neutral ligands are given in Table 7.3.

Table 7.3 Some examples of polydentate ligands

•^\;(yJ .Sid£
ntate or didentate ligand+ +i }(
Charge Donoratoms +
i. Ethylenediamine(en) t,t,,H2NiH2|H2-RE2 Zero Two N-atoms 1,2-Ethanediamine

ii. 2, 2-Dipyridyi (dipy) Zero Two N-atoms Dipyridyl

00,,,,\k,
iii. Oxalate ion O`,-be+.frjc-9€ -2 Two O-atoms Oxalato

iv. Glycinate ion ..)H2C<T-2©©?0 -1 N,O Glycinato

V, Ortho-phenanthroline(Phen)or®h)
ttN-=-_`-5r:.: Zero Two N-atoms i,10-Phenanthroline

vi. Carbonate ion -2 Two O-atoms Carbonato

o-c(::©o3
 Coordination compounds 7.9

Tridentate or terdentate ligand:

i. Diethylene triamine (dien) H2*(CH2)2N(CH2)2NH2 Zero Three N-atoms IN-(2-amminoethyl)-
€IJ 1 , 2-ethanediamine]
ii. 2, 2-2, Texpyridene (texpy) Zero Three N-atom Texpyridine

ot t foa
Tetradentate ligand:
Triethylene tttt Zero Four [N,N'-bis-(2naminoethyl)-1,
tetramine (trien) H2N(CH2)2NH(CH2)2NH(CH2)2NH2 N-atoms 2-ethanedianine]
Pentadentate ligand:
Ethylenediaminetriacetateion -3 Two N andthreeO-atom Ethylenediaminetriacetato
+:80CH2:)£iH2ngH2£(:::::::I

Hexadentate ligand:
Ethylenediaminetetraacetateion(edtal + Two N andfour0-atom thylenediaminetetraacetato

=8j:::::,iiH2iH2-i(:::::ii=
Note: Polydentate ligands have character, In terns, it is not necessary that all the do s present in the
ligandshouldformcoordinatebondwith tom/ion. For example, ls hexadentate
1igand can also function as pentadentate or tetradentate ligand with certain metal ions.

the central atom/ion through either of its donor atoms,

c. Ambidentate ligands: Certain ligands have two or more
two different complexes are formed. These complexes
[Link]
are different because they have different structures. Such
only one donor atom/ligating site coordinates to the
coordination compounds are called linkage isomers and
central atom/ion. Such ligands are known as ambidentate
the phenomenon is called linkage isomerism.
ligands,[Link]°,[Link]
ligand having two different donor atoms coordinate to Examples of certain ambidentate ligands are given in
Table 7.4.

Table 7.4 List of certain ambidentate ligands

•./`

mbidentat; Iirind \` :'^.`,\'' 8 € a . a

a, No2© N nitrito or nitrito-N M+No2©

0 isonitrito or nitrito-o rd+:oNoe
b. cNe C cyano or cyano-C M+:CN©
N lsocyano or cyano-N M+:NCO
C,
scNe S thiocyanato or thiocyanato-S M+:SCNe
N isothiocyanato or thiocyanato-N M+:NCse

d;rjt:c¥i¥:;::di=t:ee:,2:;;nN:§!t:;:;2:;;:1a:,t2:;Or€:::j|::: called bridging ligands and the complexes thus formed

are called bridged or polynuclear complexes. A bridging
ligand must have at least two lone pairs of electrons which
ligands when they are attached to two separate metal the ligand uses to get coordinated to two or more metal
atoms making a bridge between them. Such ligands are atoms. The polynuclear complex formed can be dinuclear,
trinuclear etc.
7.10 Inorganic chemistry

[Link] CheLation d. Number of rings: The complex compound having

Whencoordinationoftwoormoredonoratomsfromapolydentate maximum number of rings formed with the ligands is most
ligand to a single central atom/ion takes place forming a closed
or cyclic ring structure, it is called chelation and the ligand a :tacboL:PFL::e[XMTEpieii;]°om3Leecxai¥e(::):i3e+:So::rsttahbe):etha::
chelating ligand. The close ring compound thus formed is called 3 rings while in the latter 5 rings.
chelate or metal chelate (Chelos, Greek word means `crab'). e. Entroriy effect: The stability of the chelate complex is
Some important characteristics of chelates: explained on the basis of entropy effect. To elaborate, let us
a. Chelating effect: Chelating ligands form more stable take an example of ethylene diamine ligand (en). When one
complexes than the monodentate analogs. The complex ion/ end of `en' is coordinated, the probability of coordination
compound having such ligands does not dissociate easily. of the other end is high because this end is bound to stay
b. Formation of rings: Generally the chelate complexes close to the central atom/ion. This shows that it is easier to
with 5-or 6-membered rings are more stable. Out of these, form a chelate ring than forming coordinate bonds with two
5-membered rings are very stable when they involve independent molecules. Thermodynamically, the increased
saturated ligands, e.g., ethylenediamine which contains stability due to chelation can be attributed to an increase
5-membered stable ring structure. On the other hand in the degree of freedom of the system. Large changes in
6-membered ring structures acquire maximum stability
entropy but only small heat of reaction generally accompany
when they involve unsaturated ligands containing conjugate
the chelation process.
double bonds.
The number of donor atomsAigating atoms present in the
c. Steric hindrance: Ligands with large groups form unstable
ligand molecule which are coordinating with the central
rings than the ligands with smaller groups due to steric
atom/ion indicates the denticify of the ligand (Table 7.5).
hindrance.

Table 7.5 Some examples of chelating ligands and number of donor atoms

usga\nd. ` ` ya`/ (::a!o`\::\:a:-go`o ` Type of ligand Don®ratom .;;S I 'Examp|e§ , ;u `§O;T:';J;=;A;i§^`;;^`:;

6`8,§:2-11 i:::2-
Bidentate orDidentate 2-0 atoms H`,HI=,:.=c+:f::,H=!::,\HHHH

carbonateion A..

oxalate ion or [oX]2- B identate chelation

._,i Bidentate or 2-N atcms HH

Ill ::!=% `v : go..! Didentate

•::'::.=fi2<i:i::,\HH[Ptc12(en)I
E[::I.:jfgie£::) 7 a g)0

8
Ortho-phenanthrolinetoh)
(Or)
9,10-phenathroline

ttt Tridentate orTerdentate 3-N atoms H2fHg:l=i2t:i:±!::P'tcL(dien)]®(Tridentatech;lation)

V. NH2 CH2 CH2 NH CH2 CH2 NI12
Diethylene triamine (dien)
or [N-(2-aminoethyl)-1, 2-ethane diamine)

tTtt Tetradentate 4-N atoms H2f [H2H2rEN:`,E2t<:={::CH2-NH2[Ptcl(trien)]2+(Tetradentatechelation)

vi. iirl2tcH2j2itH tcH2>2fiH tcH2j2NH2
Triethylene tetraamine. (trien)
Or

[N,N'-big+-(2-andnoethyl)-I-2-ethanediamine.]
 Coordination compounds 7.11

f. Flexidentate ligands: Certain ligands have more than one

donor atoms like S042-, C032-, etc. which have more than
one donor sitenigating atoms. Such ligands can behave as
monodentate ligand in one complex and bidentate in another
complex. Such ligands which show variable denticity in
different complexes are known as flexidentate ligands. (It
is not necessary for a polydentate ligand to use all its donor
atoms for coordination.) For example: NH3
[CO0VH3)4(S04)]© ion (S042-as bidentate ligand)

7.4 COORDINATION NUMBER

The number of ligating atoms (of the ligands) that are directly
; -c,o3I+ , bound to the central atom/ion is known as coordination number.
It is equal to the number of sigma bonds formed between the
ligands and central atom/ion. 7t-Bonds, if any, between the
i-\,;O-S-O
NH30
ligating atom and. the central atom ion are not considered
[Link],CN°and
N2 may involve both a and 7t bonding between the central atom/
[CO(N113)5(S04)]© ion (S042- as monodentate ligand) ion and the ligating atom, it is only number of a bonds formed
which are considered in determining the coordination number
(Table 7.6).

Tabe 7.6 Coordination number (CN) of some central metal atoms/ions (Note: CN = Denticity x no, of ligands)
A. Some examples of unidentate ligands
:: t€htra] metal atom/iorii,:, y •J i-, a-,-:--:,-`:i Coma
ev

1. Aig®,C;ITS,Aiur® 2 [Agou3,2]® NH3

I 3 and 4
2. Hg2+ [H813]e, [Hg|4]2- Ie
3. cu2+} pt2+,pd2+,Zn2+,Ni°
Ni2+, Mn2+' 4
!%un#B#)~4,I;;'d[cpit4f!£:2[-Zn¥i{f2?[4*2i{'co)d g]Hd;:i©6g¥e:;eB::;e:;©
4. co2+ 4 and 5 [CO(CN)5]3-, [CoC14]2~ cN©
5. Feo 5 [Fe(CO)5] CO
6. Fe2+, Fe3+, Co3+, pt4+, cr3+,Cr°,Ni2+,|r3+ 6
8g:iecINan:'frH33ie:;:;tFv2e?;
F:{j6]E,##e2::¥];¥+],3[t[r:€S¥;,6]3+,
7. Mo4+ 7 [Mo(CN)7]3~ cNe
8. w4+ 8 IV,CN)8]4- cN©

8. Some examples of complexes with multidentate ligands. iii. [Mg(trien)C12]

i. ,co(en,3,3+ CN = Tetradentate x no. of ligands = 4 x 1 + 2 = 6
CN = Didentate x no. of ligands = 2 x 3 = 6 iv. [Mg(EDTA)]2-
ii. [Cr(dien)2]3+ CN = Hexadentate x no. of ligands = 6 x 1 = 6
CN = Tridentate x no. of ligands = 3 x 2 = 6
7.12 Inorganic chemistry

7.4.1 0XIDATION NUMBER OF CENTRAL ATOM/loN C o ordination sphere/entity

Oxidation number of the central atom in the coordination entity Cl[cr+3 OvH 3-)<8: i-\-(,--:-?i
is defined as the charge it would bear if all the ligands were i cl3\
removed along with the electron pairs that were shared with the i----i-
Cehtra| Neu- Coordi- Negative Positive Negative
central atom. It is represented in numerals (Table 7.7). metal tralun- nation unidentate uniden- counter
atoul idem- number |igand tate ion
ion tate (4+1 + 1 ligand
Table 7.7 Examples of important terms used in describing ligand -6)
coordination compounds
Coordination

.\
+ Coordirration;compound J\ [Link]. sphere/entity
ntral +etal++om- 1 Geometricalshape _,_
ic:•'at and K4:[ F I

Ni(CO)4 Ni four co 7jfrfff. Tetrahedral p.s,,,v/Central Negative Coordi-

counter
INi(C14)]2- Ni four cie 11(2+) Tetrahedral metal unidentate nation
ion
atom/ ligand number
INi(CN,4]2- Ni four cN© 11 (2+) Tetrchedral ion

pritH2O)6]2+ Ni six H20 11 (+2) Octahedral

[Coqu3)6]3+ Co six NH3 Ill (+3) Octahedral
five CNOoneF© Why NH3 form coordinate complexg while the
[CO(Ch)5F]3~ Co Ill (+3) octaliedral
species CH4 does not.

[Ago{H3)2]+ A8 two NH3 I (+1) Linear NH3 has a lone pair of electron on N hence, it can act as
'.`.`..`..`:`:[r,

Squareplanar a ligand and form coordinate complex whereas in CH4, C has no

[Cuou3)4]2+ Cu four NITS 11 (+2)
lone pair of electrons present on it, hence it cannot fom complex.

7.4.2 HOMOLEPTIC AND HETEROLEPTIC COMPLEXES

a. Homoleptic complexes are those complexes in which central
atom is coordinated with only one kind of ligand, e.g., Calculate the

[Fe(CN)6]3-. £ ...S-.?
Oxidation number is calculated as follows:
b. Heteroleptic complexes are those in which central atom Charge on complex ion = +2
is coordinated with more than one kind of ligands, e.g., Let charge on Ni = x
[Fe(H20)5NO]2+. Charge on H20 = 0
7.4.3 HOMONuCLEAR AND POLYNUCLEAR OR = Jr+6x(0)-+2
BRIDGED CoivlpLEXES
= J¥-2+
Hence oxidation number of Ni is 11.
Complexes in which only one metal is present are known as
homonuclearcomplexes,e.g.,[Co(NH3)6]3+and[Co(NH3)4C12]®.
Complexes in which more than one metal atom is present are
Calculate the oxidation number of
known as polynuclear or bridged complexes. These complexes
\:::..'...``=<.i
are fomed by bridging ligands. These complexes formed can be Let the charge on Ni be I
dinuclear, trinuclear etc. For example, 6
Charge on CNe = _I
K2INi(CN)4] + 2K© + INi(CN)4]2-
Charge on complex ion, [Ni(CN)4]2-= -2
[tH20,4Fe<::>FetH2o)r, = x+4x(-1)--2
= x-+2
... Oxidation number of Ni is 11.

OC

OC
/ CO
What is the coordination number
thecomplex[Alur20)4(OH)2]®?
[Mn2(CO)io]

Various terms discussed above may be illustrated by taking Eat::::dchi::Ilo:t:tuemoEe£[°±i#S)¥(28|4)(2:®H)2]®[Link]

some examples of coordination compounds, e.g. Charge on H20 is 0 (zero) and on OH is -1.
 Coordination compounds 7.13

Let the charge on Al be x. coordination entity is written outside the square bracket as
... j¥+Ox4+(-1)X2=+1 [Link][Co(N113)6]3+,[Co(CN)6]3-
etc.
= x-+3
... Oxidation state of Al in [Al(H20)4(OH)2]® is + 3- 9. Structural modifiers such as c!.s, fra#s etc. if present are
given in lower case as an italicised prefix. It is connected
to the formula by a hyphen.
h. Finally a counter ion could be added to the coordination
In the complex, entity to form coordination compound. If counter ion is
Ligands and their charges. positively charged species, it is written in front of the
Charge of the central ion in the comple formula of coordination entity, and if it is a negatively
What would happen ifAgN03 ls at charged species, it is written after the formula of the
0OC. coordination entity. No space is left between the counter
ion and the coordination entity.
iHHB In Complex [Fe(H20)5Cl]Br, the complex ion is
[Fe(H20)5Cl]© Note:
• Asingle
a. Ligands are 5H20 and Cle.
with the
H20isneutralligand,whereasClehasonenegativecharge.
b. Let the charge on the central ion in the complex be x.
•.. x+Ox5+(-1)-+1 • Wherethg
J¥ - +2 a. The Citation is decided by
i.e. charge on Fe in [Fe(H20)5C1]® is +2. symbol rmula of
CN, N02 and OH are
. C. [Fe(H20)5Cl]Br + AgN03i[Fe(H20)5C1]N03 + AgBr
On addition of AgN03 to the compound one mole ofAgBr
will be precipitated.

7.5 NOMENCLATURE OF
COORDINATION COMPOUNDS
Coordination compounds are considered to be produced by
addition reactions. They are therefore named on the basis of
`additive principle' . The name is built up around the central atom

just as the coordination entity is built up around the central atom.

For example, addition of ligands to a central atom:
Co3++6NH3-[CoO{H3)6]2+,additionofligandsnametothe
central atom/ion is hexaamminecobalt(Ill).

7.5.1 RULES FOR WRITING THE FORMULAE FOR i. Ionic charges and oxidation numbers: If the formula of a
MONONUCLEAR COORDINATION COMPOUND charged coordination entity is to be written without that of
Sequence of symbols within the coordination formula is governed the [Link] ion, the charge is indicated outside the square
by the following rules: bracket as a right superscript, with the number before
a. The central atom is listed first followed by the ligands. the sign. The oxidation number of a central atom may be
represented by a Roman numeral, which should be placed
b. The ligands are listed in alphabetical order of the ligating
as a right superscript on the element symbol.
atoms (charge of the ligand is not considered when deciding
the order and the charge of the ligand is not written in the Examples:
formula). i. [Ptc16]2- ii. [Cr[[[ C13(OH2)3]

c. The formula for the entire coordination entity is enclosed iii. [Cr(OH2)6]3+ iv. [Fe[](CO)4]2~
is square brackets.
V. [Cr[][OVCS)4 0VH3)2]e
d. When the ligands are polyatomic (i.e. contain more than one
atom) their fomulae are enclosed in parentheses. Ligand 7.5.2 RULES FOR WRITING THE NAME OF
abbreviations are also enclosed in parentheses. MONONuCLEAR COORDINATION COMPOUND
e. No space is kept between representations of ionic species The mles as recommended by IUPAC (International Union of
within the formula. Pure and Applied Chemistry), revised in 2005, being followed
f. When the formula of a charged coordination entity is while naming a mononuclear coordination compound are as
to be written without the counter ion, the charge of the follows:
 7.14 Inorganic chemistry

i. If the coordination compound is molecular or non-ionic a (hydrazinium), NO© (nitrosonium), N02® (nitronium)
single word name is given. etc.
c. Negative ligands (organic or inorganic): These type
ii. If the coordination compound is in the fom of salt or ionic,
name of the cation is given first, followed by the name of the
#]2%a(nni:r:;,dj9-{;?o')e692.2_Cto¥o(xcoy):no°!6(:Lop:::i°or)?)'
anion in accordance with the usual nomenclature scheme.
If the name of the anioni.c ligands ends in -ide, -ite or
A space is left between the cationic and anionic part. -ate, the last `e' is replaced by `0' giving -ido, -ito or -
iii. In the coordination entity, name of the ligand is written first ato e.g. S042-(sulphato), NH2°(amido), ON0°(nitrito)
followed by the name of central metal atom/ion. etc.

iv. Order of naming ions: The positive ion (cation) is named d. Organic ligands: Organic free radicals are given their
first followed by the negative ion (anion) irrespective own names, e.g. CH3.(methyl), (C2H5.) (ethyl). For
organic neutral molecules, their names are used. e.g.,
of whether cation is complex or anion is complex. The
P(C6H5)3, triphenyl phosphine, C6H5N pyridine (py)
complex part is written as one Word e.8., [CO(NH3)6]C13,
etc. (refer Table 7.8).
hexaamminecobalt(III) chloride.
Note: Enclosing marks `( )' are requrfed for (a) neutral and
v. Naming of ligands: Different types of ligands are named
cationic ligand names (however, co uch as
differently (refer to Table 7.8).
aqua, ammine, carbonyl, nitrosyl,
a. Neutral ligands: These type of ligands have no special require enclosi arks, unless tier
ending and are used as such except for NH3 (ammine), inorganic ands containing 1
H20 (aqua), CO (carbonyl), CS (thiocarbonyl) and NO as triphosphato); (c) for any compositional name (such as
(nitrosyl). carbon disulfide); (d} for any substituted onganic ligand (even
b. Positive ligands: These type of ligands are used as if there is no ambiguity in its use); (e) and wherever necessary
such. These generally end in -ium, e.g., H2N - NH3© to avoid

Table 7,8 List of neutral, positive and negative ligands

^ . r .seji7`*,t`> 2```\r`h'\ `

+:0: y>^beriti€ftyt^ ` I,gand ,\ :;;¥:to::; `€ \ ChangeA-s,L3

~Si%c,,``?g) ^,,/
eS,~ -*y, .giv
ire,\¥,hs €qu*Iexv a ^ <:y§Sfi``?a:,ng^`€tL:\ ^``,,t aepm \ , \OL+`2`:;y¥+ ,,

Neutral ligands Water H20 •0

Aqua/aquo 0
Ammonia NH3 0 Jinine N
Carbon monoxide CO 0 Carbonyl C
Nitrogen oxide NO 0 Nitrosyl N
Thidcarbonyl CS .0 Thiocarbonyl S
Thionitrosyl NS 0 Thionitrosyl N
Monodentate Pyridine (py) C5H5N 0 Pyridine toy) N
Methyl amine CH3NH2 0 Methylanine N
Dinitrogen N2 0 Dinitrogen N
Dioxygen 02 0 Dioxy8en 0
Phosphine PH3 0 Phosphine P
011H2N{-NH2
Urea 0 Urea 0
S11H2N+NH2
Thio-urea(tu) 0 Thio-urea S

Triphenylphosphine Ph3P 0 Triphenylphosphine P

Acetone CH3COCH3 0 Acetone 0
Bidentate Ethylenediamine (en) (abidentateligand) NH2(CH2)2NH2 0 Ethylenediamine (en) 2 N-atoms

Tridentate Diethylene triamine 0 Diethylene triamine 3 N-atoms

H2fT.TiH2H2C-E2EfH2
(dien) (diene)

llRE:-t`_:#EE±L|Ettfl,£.r`j]jLj__,.,__,_+,.,,t====
 Coordination compounds 7.15

Tetradentate Triethylene tetramine 0 Triethylene tetramine 4N-atoms

H2f-NH(CH2)2NH2H2c-RE(en2)2#H2
(trien) (trien)

Positive ligands
Monodentate Nitrosoniun ion No® +1 Nitrosonium N
Nitronium ion N02© +1 Nitronium N
Hydrazinium ion NH2NH3® +1 Hydraziniun N
Negative ligands
Monodentate Hydride ion H© -1 Hydrido H
Oxide ion o2- -2 Oxo 0
Peroxide ion 0'_2- -2 Peroxo 0
Perhydroxide ion 0,,,- -1 Perhydroxo 0
Hydroxide ion ©OH -I Hydroxo 0
Fluoride ion FO
-1 Fluoro (fluorido) F
Chloride ion cle -1 Chloro (chlorido) Cl
Bromide ion Bra -1 Bromo (bromido) Br
Iodide ion 10
-1 Iodo (iodido) 1

Acetate ion CH3Ccoe -1 Ac etato (acetatide) 0

Cyanide ion cNe -1 Cyano (cyanido) C
Isocyanide ion N©=C©
-1 Isocyano N
Sulphite ion s032- -2 Sulphito 0
Sulphide ion s2- -2 Sulphido or thio S
Hydrogensulpbite ion HSO1©
-I Hydrogensulphito 0
Amide ion NH2© -I Amido N
Imide ion NH2- -2 Imido N
Nitrate ion NO?O
-1 Nitrate N
Nitro ion -1 Nitro (nitrito-N) N
No2©(M+N<:,

Nitrito ion ONO© (M + O-N=O) -1 Nitrito (nitrito-O) 0

Nitrido io.n N3- -3 Nitrido N
Azide ion N30 -1 Azido N

Cyanate ion cNO© -I Cyanato 0

Isocyanate ion OcNO -I Isocyanato N
Thiocyanate ion °SCN (M + SCN) -1 Thiocyanato S

Isothiocyanate ion ENCS (M + NCS) -I. Isothyiocyanato N`

Hydrogen carbonate ion HC03e -1 Hydrogencafbonato 0

Bidentate Acetyl acetonate ion CH3fiiH=C+H3ob© -i Acetylacetonato(Acac) 2 0-atom

Glysinate ion NH2-CH2100° -1 Glycinato(gly) 1 N-atom and 1 O-ato

Sulphate ion s042- -2 Sulphato 2 0-atom

Thiosulphate ion s2032- -2 Thiosulphato 2 0-atom
7.16 Inorganic chemistry

Dimethylglyoxine 0 CH3f=k3CH3C-N:OH -I Dimethylglyoxiomato 2 N-atom

oxalate ion c2042- -2 Oxalato 2 0-atom

Carbonate ion c032- -2 Carbonato 2 0-atom
Pentadentate Ethylenediamine triac- -3 (EDTA3-) 2 N-atoms and 3 0-
etate ion fH2~it(CH2C0092CH2-RECH2COo° atoms

Hexadentate Ethylenediamine tot- rd (EDTA1 2 N-atoms and

raacetate ion 4 0-atoms
fH2N(CH2COB2CH2It.(CH2COD2

vi. Within the coordination sphere, if more than one kind of The complex [CoC12avH3)4]® is
ligands are present, they are listed in alphabetical order Tetraamminedichloridocobalt (Ill)
(irrespective of their charge) before the name of the central ix. The oxidation state of the central metal atom/ion is expressed
atom. Numerical prefixes which indicate the number of in roman numerals, which is added at the end of the name
ligands are not considered in determining that order. of metal atom/ion and enclosed in bracket. No positive sign
For example, is used. For example,
[PtcIBrov02) OVH3)]° [Co(NH3)6]2+ Hexaamminecobalt (Ill) ion
Amminebromidochloridonitroplatinate (11) I. When the coordination entity is anionic or negatively
[CocloJH3)5]2- charged the name of the central metal atom/ion ends with
Pentaamminechloridoc obaltate (Ill) suffix `ate', i.e., the name of coordination entity ends in
{ate'.
vii. Prefixes: Number of ligands in the coordination entity
is indicated as numerical prefix. Two types of numerical For certain elements their latin name is used, e.g.,

prefixes are used. Examble' \ ameinpositwe/ + Namein anionic or

' Heg*give €ptry^pL€* yt .
a. di, tri, tetra, penta etc. (mono is generally omitted). neutralcomplex +
Multiplicand is not enclosed in parentheses. This A8 Silver Argentate
is used for simple ligands.
Pb Lead Plrmbate
For example,2 C1° -dichlorido
3 NH3 - triammine Au Gold Auete
b. bis, tris, tetrakis, pentakis etc. Multiplicand Hg Mercury Mercurate or hydra-
is enclosed in parenthesis. This is used for zinate
complex ligands, i.e., when the name of the Ni Nickel Nickelate
ligand is lengthy or complicated ®o|ysyllabic or
Fe hen Ferrate
multiplicative prefixes are already present in the
ligand) xi. If the coordination entity is positively charged or neutral, it
(CH3NH2)2 B i s (methylamine) has no special ending. For example,
[Co(CN)6]3-Hexacyanocobaltate (Ill) ion.
xii. Stereochemical descriptors: For coordination number
Tris ( 1, 2-ethanediamine)
(::==:)3 greater than one, different geometrical arrangements of
the atoms attached to the central metal ion are possible.
H3c-firf+H3 A descriptor is used to differentiate between isomers. The
descriptor is indicated as an italicized prefix, in lower case.
It is connected to the name by a hyphen.
( HBis(dimethylglyoximato)

For example,
viii. The final vowel of the numerical prefix is not omitted. (mono
is an exception) is named as cz.s-diaminedichloridoplatinum (11)
mono + oxide + (monoxide) xiii. Naming of the optical isomers: Dextro and Levorotatory
Example: #_;}4 =:t:::#e]ne optically active compounds are respectively designated
either by (+) and (-) or by d- and /; e.g., dextrorotating
 Coordination compounds 7.17

K3 [Cr(OX)3] is named as potassium (+) trioxalatochromate 0

a. [ovH3)5cO+3i6]HrdjdiH3)5]+5c];lx5
(Ill) or potassium d-trioxalatochromate (Ill).
xiv. Naming of the linkage isomers: If necessary, the point of is given the name as
attachment of the ligand to the central metal is expressed
A-hydroxo-bis ®entaamminecobalt (Ill)) chloride
by the symbol of element attached in italics after the name -I-1 -I

of the ligand and separated by a hyphen. +2Cl

p_t<poEt3
1 . \ TO`O
i oroT\alo'm.. + Name of the i:
a
++
*8

|''y::^seg¥as\p^&Ovgr%g*ae4g:93%.€exy\j\^:r, ga\¢ ,, ,< (cz.I-di-#-chloridobis(chlorotriethylphosphineplatin

+:scNe S Thiocyanato-S un (11))
00o

+:NCse N Thiocyanato-N
c. o:€:3Foe€:§>F:€§§
+:cNe C Cyano-C

+:Nco N Cyano-N
Tri-#-carbonyl bis(tricarbonyliron(0))
0,0 Dithioxalato-0-0'
7.5.4 POLYNuCLEAR COMPLEXES
I;>c-c<T Polynuclear complexes having M-M bond can be sylnmetrical or
JJ unsymmetrical. In such complexes the rules followed to write the
0,S Dithioxalato~O-S name of the complex are as follows:
i. In case of symmetrical complex, the names are generally
I:>c-c<i`=T given with the use of multiplicative prefixes like di-, tri-,
tetra-, etc.
S,S Dithioxalato-S-S,
Forexanple,[(fo)5rfu-rfu(€O)5]
B i s ®entacarbonylmanganese(0))
[!>c-<T ii. In case of unsymmetrical complex, one of the central
atom and ligands bonded to it are considered as the ligand
For exaniple: [Co(N113)5 (N02)]2+ has two isometric
to the other central atom.
forms having red and yellow colours. 0000
1. The red colour isomer [Co(NH3)5 (ON02)]2+ is For example, [(CO)4CO - Re(CO)5]
named as pentaamminenitrito-O-cobalt (Ill). Pentacarbonyl (tetracarb onylc obalt(O))ruthenium (0)
2. The yellow isomer [Co(NH3)5 (N02)]2+ is named as
7.5.5 STABLE 0XIDATION STATE (OS): SOME OF THE
pentaamminenitrito-N-cobalt (Ill)
TRANSITION METALS OF THE THREE SERIES
7.5.3 BRIDGING LIGAND
These stable OS would be helpful to find the oxidation states of
It is defined as the ligand which bounds to two or more central the metal ions while naming complexes having cation and anion
atoms simultaneously giving a polynuclear complex, e.g. both as complexes.
[(N113)5 CocOH-Co0VH3)5]C15 (-OIP acts as bridging ligand) i. First transition series:
r,£G-,JNi` ,
When bridging ligand is present within the complex, : Ti y , | elf A in •\Fe(„
u\+ -Zn
following points are noted for the nomenclature of these +3 +2, +2' +2, +2! +2' +2, +2' +I, +2
complexes: +3 +3 +3 +3 +3 +3 +3 +2
i. Bridging ligand is expressed by greek letter `H' which
+4 +4,+5 +6 +4'+7
is added immediately before the name of the ligand and
separated by a hyphen.
ii. Second transition series:
fi. The number of bridging ligands are expressed as:
y \zr : rdS ( Mo-
di-# (Two bridging ligands)
+3 +4 +3'+5 +6 +4,+6 +3 +3 +2,+4 +I +2
Tri-A (Three bridging ligands)
bis-/ (Two polysyllabic bridging ligands)
+7
ffi. The bridging ligands along with non-bridging ligands are
iii. Third transition series:
generally written in alphabetical order unless the symmetry
of the complex permits the simpler name by the use of La +a-J : . rw` Rg-:
multiplic ative prefixes. +3 +4 +5 +6 +4' +3, +1, +2, +1' +1,
iv. If the same type of ligand is acting as bridging as well as +6 +4 +3 +4 +3 +2
non-bridging ligand, the bridging ligand is expressed first. +7 +6 +4
Following examples illustrate the above points:
7.18 Inorganic chemistry

Table 7.9 lupAC name of some complexes

a.

I. [coon3)6]ci3 Hexaamminecobalt(Ill) chloride

2. [Cr C12(H20)4] N03 Tetraaquadichlorido chromium (Ill) nitrate
3. [CocloJ02)qu3)4]N°3 Tetraarprninechloridonitrito-N-cobalt(Ill) nitrate
4. [Cr(en)3]C13 Tris(I,2-ethanediamine)chromium(Ill)chloride
5. [COC12(en)2] (S04)2 Dichlorido( 1,2 -ethanediamine)cobalt(II) sulphate
6. Na3[Fe(C204)3] Sodium trioxalatofeITate(Ill)
7. [CoBro¢H3)4(H20)]qu03)2 TetraammineaquabromidoocobaltqlI) nitrate
8. [Cr(H20)6]C13 Hexaaquachromium(Ill) chloride
9. [CoC1(ONO)(en)2]® Chloridobis( I, 2 -ethanediamine)nitrito-O-cobalt( Ill) ion
10. [Crc12(H20)4]Cl Tetraaquadichloridochromium(Ill) chloride
11.
[CO(C03)qu3)5]C[ Pentaamminecarbonatocobalt(III) chloride
12. [Ir(en)20+H3)2]C13 Diammine bis( I, 2-ethanediamine)iriduim(Ill) chloride
13. [CoclquH3)4N02]C104 Tetraamminechloridonitritocobalt(Ill) perchlorate
14. [Agqu3)2]Cl Diamminesi lver(I) chloride
15. [CoBrcl(en) (ONO)2]® Bromidochlorido( i, 2-ethanediamine)dinitrito -0 -cobalt (Ill) ion
16. [Co(en) qu3)2 Brcl] N03 Diaminebromidochlorido(ethylenediamine)cobalt(Ill)nitrate
17. [Cocl(en)20NO]© Chloridobi s (ethylenediamine) nitrito-O-cobalt(Ill) i on.
18. [coorH2)2qu3)4]oc2H5 Diamidotetraamminecobalt(Ill) ethoxide
19. [CON30¢H3)5]S04 Pentaammineazidocobalt(Ill) sulphate
20. [Co(en)3]2 (So4)3 Tris(1,2-ethanediamine)cobalt(Ill)sulphate
21. [Cr(H20)6]C13 Hexaaquachromium(III) chloride
22. [RUQ¢H3)5N2]C12 Pentaamminedinitrogermithenium(II) chlori de
23. [Coqucs)quH3)5]C12 Pentaammine-thiocyanato-N-cobalt(Ill) chloride
24. [Co(ONO)quH3)5)]S04 Pentaamminenitrito-O-cobalt(Ill) sulphate
•- b. (:
[uRAC name
25. K3[Fe(C204)3] Potassium trioxalatoferrate (Ill)
26. K2[CO(CN)5Q¢O)] Potassium pentacyanidonitrosylcobaltate(Ill)
27. K[Ptc13Ou3)I Potas sium amminetrichloridoplatinate(II)
28. Na2[CroF4] Sodium tetrafluoridooxochromate (IV)
29. Na2[SiF6] Sodium hexafluorido silicate(IV)
30. [Hg[Co(SCN)4] Mercuric tetrathiocyanatocobaltate(II)
31. K4INicN)4] Potas sium tetracyanohickelate(0)
32. Dextro K3[Ir(C204)3] Potas sium d-trioxalatoiridate(Ill)
33. Li[AIH4] Lithium tetrahydridoaluminate(Ill)
34t oun4)2[pt(SCN)6] Ammonium hexathiocyanatoplatinate (IV)
35. K3[COOv02)6] Potas slum hexanitritocobaltate(Ill)
36. K3[Coqu02)6] Potas s ium hexanitritocobaltate(III)
37. qu4) [crQJH3)2arcs)4] Ammonium diamminetetrathiocyanato-N-chromate(Ill)
38.
[CO(H20)3C12(C03)]e
Triaquacarbonatodichloridocobaltate(Ill) ion
39. Tetrakisdiethylamidochromate(Ill) ion
[Crqut2)4]e
40. K2[OSC15N] Potas sium pentachloridonitridoosmiate(VI)
41. K3[Fe(CN)6] Potas sium hexacyano ferrate(Ill)
42. K4[Fe(CN)6] Potas sium hexacyanoferrate(II)
43. Na[Boro3)4] Sodium tetranitratoborate (IV)
 Coordination compounds 7.19

44. Na3[A8(S203)2] Sodium bis(thiosulphato)argentate(I)

45. K[B(C6H5)4] Potassium tetratobenyl)borate(Ill)
46. K[Sbc15C6H5] Potassium pentachlori dotohenyl}antimonate(V)
47. K[Ptc13(C2H4)I Potassium trichlorido(ethylene) platinate(II)
48. Na2[Fe(CN)5NO] Sodium pentacyanohitrosylferrate(II)
49. K3[Fe(CN)5CO] Potassium carb onylpentaeyanoferrate(II)
50. Na3[cooro2)6] S o drum hexanitrito-N-cobaltate(Ill)
51. K3[Al(C2°4)3] Potassium trioxalatoaluminate(III)
52. Ca2[Fe(CN)6] C alcium hexacyanoferrate(II)
53. Na[Co(CO)4] S odium tetracarbonylcobaltate(-I)
54. 0{H4)3[Crqucs)6] Ammonium hexathio cyanato -N-chromate(Ill)
55. K3[Cr(CN)6] P otass ium hexacyanochromate(Ill)

Note: For CNe either cyano or

se
REutralcompleae§€ig\-;;~;z3ngasxaeLgsevetsdr§\.`°ae";x;.}t^

56. INi(C04] Tetracarbonylnickel(O)

57. [coquo2)3orH3)3] Triamminetrinitrito-N-cobalt(Ill)
58. [Ptc120VH3)2] Diamminedichloridoplatinum(II)
59. [Cr(Pph3) (CO)5] Pentacarbonyltriphenylpho§phinechromium(O)
60. [Ni(din8)2] Bis(dimethylglyoximato)nickel(II)
61. [Mn3(CO)2] Dodecacarbonyltrimanganase(O)
62. [CrovH3)OJ02)3] Triamminetrinitritochromium(Ill)
63. [CuC12(CH3CH2)2] Dichloridobis(methylamine)copper(II)
64. cis-[Ptc12(PEt3)2] cis-dichloridobis(triethylphosphine)platinumqu)
65. [Cu(Sly)2] Diglycinatocopper(H)
66. [CuC12(0=Cqu2))2]C12 Dichloridobis(urea)copper(Il)

mpieh £inta`inin£`cationi€and:`,°~,`` i
£+\a,`g\+
as. '+ #se8Ry#*`i§' uv•gr2sg&S'$3§xpes`2

x^c

ar €,J,J
6 {6r,`vzS`.` ,xa` 5 ; Sr%.s{,#Vi32`

67. [Ptc12quH3)4] [Ptc14] Tetraamminedichloridoplatinum(IV) tetrachloridoplatinate(ID

68. [COC12qu3)4]3 [Cr(CN)6] Tetraamlninedichloridocobalt(Ill) hexacyanidochromate(Ill)
69. Ptqu3)4] [Ptc14] Tetraammineplatinum(II) tetrachloridoplatinate(II)
70. [Cr(en)3] [Fec14]3 Tris( 1,2-ethanediamine) chromium(in) tetra-chloride ferrate(Ill)
71. [Pt®y)2] [Ptc14] Tetrckis(pyridine)platinum(II) tetrachloridoplatinate(II)
i(-`\\ Efi
`k;y,r{^,r ^*uF&€:name t^t „ ` „` «es*Leo
a. dge complexes +
72. [qu3)5Cr-OHcrqu3)5]C15 H -Hydroxobis®en'taamminechronium(Ill) chloride
73. Di-u-hydroxobis(tetraaquairon(Ill) sulphate

[H20)4Fe<:=>e(H20)I(S04)2
74. H-Amido-pr-nitritobis(tetraamminecobalt(Ill)) nitrate

pr3j4c<:22~`Oqu3,]Or03,4
75. Potassium bis(thiooxalato-O-O ')nickelate(II)
K2

76. Thinsulphato-O-O' -thiosulphato-O-S -platinate(II) ion

[:,s=:=p<:=s=:]2-
7.20 Inorganic chemistry

77. Tris-H-carbonylbis(tricarbonyliron(0))
o:c:3Fe€:§>Fe€:i
78.
(C6H5):PL)P<::>Pt<:(Lc6H5)3 trans-Di-pr-chloridobis(chloridotriphenylphosphinaplatinum(II)

79. I(CO)5Mn~Mn(CO)q] Bis®entacarbonylmanganese(0))

80. H -Peroxo+I-superoxobis(tetraamminechromium(Ill) bromide

[H3fty4Cr+3<::;>Cr+3qug)4]+3Br;3
81. Di-pr-peroxobis(tetraamminechromium(Ill)) perchlorate

[qu3)4Cr<::>Crqu3)I(Clo4)2
82. Di-pr-superoxobi s(tetraaquacobalt(IIl)) perbromate

[H2o)4cO<::>cO(H2o)4](Bro4)4

Table 7.10 Names and structures of some abbreviations used in complexes

`, x zxl,`\7o8i3,a Z` \`XS`z`x' , \ ~Xsrrz+ lz;'t2gz,as \`gS Ziz;r^Si,'-` s2;=sos¢;^,`,8 {S'vrng + S`as ^`aer}ff'se
',-,-,:.i;,`;;4;,i:-I

•yr [Link]. , ,,
€:?;%<ov::€+;€;€£=`;1,,`t'*`Abbre atione `„ \ ^[Link].`; t*: , ` y, h;2?t,,x,,o>.,o`3svf3. c`ccue`u qu»t,fz I ,,|i3°J„!„.frsj.=y;¥t¢J6€&7~:r:,[Link]," `¥;nse

1. acac® o©o
Ill

Acetyl acetonato ion [CH3i€H-CngH3]

2. acacH OHO
Ill

Acetylacetone [CH4i±HTC-CH` ]
3. am Ammonia our3)
4. aq Aqua (H20)
5. big NHN©
1111

Biguanido ion [H,N{~NH{-NH,] .

6. • big H NH , NH
1111

Biguaride [HONLC=NHLC-NH9 ]
7. dien Diethylentriamine QTH,|CH,),-NH|CH,),-NH,
8. DMGe DimethylglyoximatoionH3Ci=N~OH
H3Ci-N`cp
9. DMGH DimethylglyoximeH3Ci=N+OH
H3C-C=N`oH
10` EDTA4- Ethylenediaminetetraacetatoion

::::::::=NicH)2-N=::;::::
11. EDTAH4 Ethylenediaminetetraaceticacid
12. en Ethylenediamine
13. eten N-ethylethylenediamine [H2NicH2)2-NELC2H5]

14.
gly©
GlycinatoionOu2{H2{009
15. glyH Glycine
16. IDA2-
©OociH,-NlreH7100©(Imidodiacetatoion)
17. IDA H' Imidodiacetic acid
18. ox2- Oxalato ion Poociooe]
 Coordination compounds 7.21

19. OXH' Oxalic acid

20. tetraen Tetraethylenepentamine
21. trien Triethylenetetramine
22. ph Ortho-phenthroline
23.` Pn 1 , 2-Diaminepropane
24. tn 1, 3-Diaminepropane

Table 7.11 Formulae of the coordination compounds

s.N®. Name Formula ` , y:

1. Sodium pentacyanonitrosylferrate(Ill) Na2[Fe+3(cN~5)5NOor2

2. Hexakis(ethanenitrile)iron(II) chloride i [Fe(CH3CN)6]C12

3. Pentaamminedinitrogenruthenium(II) chloride [Ruo¢H3)5or2)]cl2

4. Tetraethylammonium diamminetetrathiocyana- Q¢Et)4[CrquH3)2qucs)4]
to~N-chromate(Ill)
5. Triamminecarbonatodichlorido cobaltate(Ill) ion [coci2tco3)orH3J3]®
6. Ammonium hexathio cyanato-S-platinate(IV) OJH4)2[Pt(SCAN)6]

7. trams-diamminedichloridoplatinum(II) H3gl=pt<=3

8. Ammoniumtetraamminediisothiocyan;to qu4) [crorH3)4orcs)2]

chromate(Ill)
9. Tetranmminechloridothiocyanato-N-cobalt(Ill) [cocloun3)4qucs)]No3
10. Tetrachlorido( I , 2~ethanediamine) platinum(IV) [Ptc14(en)]
11. Sodium diamminetetracyanochromate(Ill) Na[(CrorH`),(CN)4]
12. Sodium ethylenediaminetetraac€tato Na2gNi(edta)]
nickelate(II)
13. Potassium tetraeyanonickelate(0) ' I K4INi(CN)4]
14. Amminebromidochloridomethylamine PtBrclqu3)(CH3NH2)]
platinum(II)
15. cis-tetraamminedichloridocobalt(Ill) chloride 1 Cl
i H3:L>¢o<RE; ci
NH3

16. Tetraaquadichloridochromium(Ill) nitrate [Crc12(OH2)4]N03

17. Ammonium aquapentafluoridonickelate(IV) quH4) INiF5(H,O)I
18. Bromidodichloridoididoplatinate(IV) [PtBrc12I]
19. Magne sium hexacyanoferrate(II) Mg,[Fe(CN)d
20. Potas`sium tetraoxo ferrate (IV) K4[Fe(O)4]
21. Potassium tetrazido cobaltate¢I) K,[CoOV1)4]
I INicl?(Pph?)?I
22' Dichloridobis (triphenylphosphine) nickel(II)
23. Chloridocarbonylbis(triphenylphosphine) [|rcICO(Pph3)2]
iridiun(I)
24. Hexaamminecobalt(III) dianiminetetrachlorido [cOoun3)6] [crcl4ou3)2]
chromate (Ill)
25. Hexaammirmickel(II) hexanitrfuocobaltate(Ill) INiqu`)6 [cooro,jf,]
26. Tetraamminedibromidocobalt(II) [C0Br2Ou3)4] [Znc14]
tetrachlororidozincate(II)
27. Tenanminesulphatocobalt(Ill) nitrate [cOoun3)4(so4)]No3

L
7.22 Inorganic chemistry

28. Triamminechloridocyanonitritocobalt(Ill) [CoC1(CN)QVH3)3qu02)I

29. Tetrathiocyanato~N-zihe(II) ion [znorcs)4]2+

30. Tetrathiocyanato -S-cadmium(II) ion [Cd(SCN)4]2+
31. Lithium tetrahydridoaluminate(Ill) Li[AIH4]

32. Potassium amminetricyanooxoperoxochromate K2+2[cr+5(cN-3)3O-2(02)~2NH3r2

(V)
33. Potassium amminetrieyanooxosuperoxochro- K2+2[cr+4(cN-3)3o-2(o2)JNI3r2
mate (IV)
34. Calcium oxoperoxosuperoxotri aquachromate Ca+2[Cr+3(H20°)30-2(02)-2(02)-]]-2
(Ill)
35. Potass ium oxodisup eroxctriaquachromate (Ill) K+][Cr+3(H20°)30-2(02)2~]X2]-I

36. Aluminium oxodisuperoxo triaqua chromate Al+3[Cr+3(H20°)30-2(02)2~2X2]-3

(Ill)
37. Bis (cyclopentadienyl) iron (11) [Fe(C5H5)2]

38. Dibenzene chromium (0) [Cr(C6H6)2]

.39.
Ammonium heptafluoridozirconate(IV) QVH4)3 [ZrF7]
40. Tetraaquadibromoidochromium(Ill) chloride [Cr(H20)4Br2]Cl

e. Potassium tetracyanoouprate(II)
f. Tetraanminediaquanickel(II) sulphate
Write the formula for the fcmowing coordination compounds. Tetraaquliehloridoiron (Ill) i on
I. a. Tetraanineaquachlorido cobalt (Ill) chloride Potassium
b. Potassium tetrahydroxozincate (11) P entachloridoazidoosmiate (IV) ion
c. Potassium trioxalatoaluminate (Ill) TriaquachlQridoplatinun(H) bromide.
d. I)ichloridobis (ethane-1, 2-diamine)Cobalt(Ill) ion +2-I
REffiue a. [z+n2(off)4]2~ b. [[Link](H20)°5]Cl-I
UPAC names of the coordination 00

compounds.
c. [C+u2Br#- d. [Fe(CO)5]
+24 +20
K3[Cr(C204)3] e. K2[Cu(CN)4] f. INi (H20)20VH3°)4] (S04)-2
c. [CoC12(en)2]Cl d. [Coqu3)5(C03)]C1
e. 9. [F+e3C|2-2(H28)4]© h.K+33[c+r3(c;2oX:)3]-3
+2 -I 0 -1
illffiHEN I. a. [CoOu3)4(H20)Cl]C12 i. [O+s4C|5-50J3)-]]2- j. [Ptc1(H20)3]Br
b. K2[Zn(OH)4] I C. K3[A1(C204)3]
d. [CoC12(en)2]® e. INi(CO)4]
11. a. Diamminechloridonitrito-N-platinum(II)
Name the following complex ions:
b. Potassium trioxalatochromate(Ill)
a. [PdBr4]2~ b. [cucl2]©
c. Dichloridobis (ethane-1, 2-diamine) cobalt(Ill)
c. [Au(CN)4]® d. [AIF6]3- `
chloride
d. Pentaamminecarbonatocobalt(III) chloride e. [CrquH3)6]3+ f. [Znou3)4]2+

e. Mercury tetrathiocyanatocobaltate(Ill) 8. [Fe(CN)6]3~

illEEHB a. Tetrabromidopalladate(II) ion

b. Dichloridocuprate(I) ion
Write the formula for the following coor-dination compounds. c. Tetracyanoaurate(III) ion
a. Tetrahydroxozincate(II) ion d. Hexafluoridoaluminate(Ill) ion
b. Pentaaquachloridochromium(II) chloride e. Hexaamminechromium(Ill) ion
c. Tetrabromidocunraterll\ ion f. Tetraamminezincate(II) ion
9. Hexacyanoferrate(Ill) ion
 Coordination compounds 7.23

7.6 WERNER'S COORDINATION iii. .Ligands are directly attached to the metal atom/ion by
secondary valency and are shown by thick line (-).
THEORY iv. In modem terms, while writing the structure ofa complex
Alfred Wemer is known as father of coordination chemistry. species satisfying the secondary valence and metal are
Wemer's coordination theory (in 1893) was the first attempt to written inside the coordination sphere (represented by
explain the bonding in the coordination complexes. This theory and []).
his painstaking work over the next 20 years won Alfred Wemer, v. Secondary valencies are directional in character, since
the Nobel Prize in chemistry in 1913. the species satisfying the secondary valency (i.e.
The chief methods available to Wemer for the investi-gation Iigands) are directed towards the fixed position in space,
of complexe; were the study of chemical reactivity, electrical which gives rise to characteristic spatial arrangement
conductivity and isomerism. The following example, taken from
corresponding to different coordination numbers.
his work illustrate their applications by the action of oxidising
Such spatial arrangements are called coordination
agents on solution of cobalt (11) chloride in the presence of
ammonia the following compounds are formed. po|yhedra.
Wemer observed that every element must satisfy all its
+S. dein,pndirdtt^`^^ y [Link] REPE?¥o(-' ) €ryS±€rfei€ ?-,. primary and secondary valencies.
No.+
y chl®[Link] condut•tivdy: slHdies. ` :;.i?. In order to meet this requirement the negative ion may
have a dual behaviour, i.e., in satisfying the primary
valency and in satisfying the secondary valency.
byAgN03
Further the ligands which satisfying the secondary
1. CoC13.6NH3Leutiocobalticchioride(yellow) 3 6 charges 4 particles valencies must point out in definite directions in space
whereas the primary valencies are non-directional
in nature. Thus the presence of secondary valencies
attribute to the isomerism in inorganic complexes, i.e.,
2. CoC13.5NH3.H20Roseocobalticchloride(Red) 3 6 charges 4 particles stereoisomerism.
ThusonthebasisofwemertheoryCoC13.6NH3iscalled
hexammine cobalt (Ill) chloride because there are six
3. CoC13.5NH3Purpureocobalticchloride(Puxple) 2 4 charges 3 particles aqunonia ligands and the cobalt is in the +3 oxidation
state, i.e. cobalt has three primary valencies and six
[Link] valencies.
4. CoC13.4NH3Vloleocobalticchloride(Violet) 1 2 charges 2 particles Siriilarly, other complexes of cobalt and ammonia such
as CoC13.5NH3, CoC13.4NH3 and CoC13.3NH3 Can be
represented as follows.
5. CoC13.4NH3Paraseocobalticchloride(Green) 1 2 charges 2 particles
H3N\
7.6.1 MAIN POSTULATES OF WERNER'S THEORY

To explain the above observations, Wemer proposed Wemer's

coordination theory. Its postulates are:
1. A metal possesses two types of valencies:
H3N \
NH3

[CO0JH3)6]C13
Cl
NH3
H3N-
cl,,
NH3

[C00VH3)5C1]C12
a. Primary or ionisable valency ( ...... )
i-I//\ H3C
b. Secondary or non-ionisable valency (-) H3N\
2. Characteristics of primary or ionisable valency:
Co -Cl
i. It corresponds to the oxidation state of the metal atom/
ion or charge carried by the metal ion in the compound.
ii. Primary valence of the metal ion is neutralised and H3N
/1!\ di NH3 H3N
/li\ t;1 .NH3
satisfiedbynegativeionsuchasC1°,S042-etc.
[COC120VH3)4 C12]Cl [CO0JH3)3C13]
iii. The attachment of metal ion with the negative ligand is
shown by dotted lines ( ---- ). It is clear from the above formulae that complex compound (as
3. Characteristics of secondary or non-ionisable valency: given by Wemer), has one characteristic feature, i.e., some of the
i. This corresponds to the coordination number of the negative ligands such as chlorine has to perfom two functions in
satisfying both the primary and secondary valencies and is shown
metal atom or ion.
to be attached to the metal ion by dotted and thick lines. Such
ii. Secondary valencies may be satisfied by either negative
valencies which perform a dual role are not ionised.
ions or neutral molecules.
7.24 Inorganic chemistry

Thus the above compounds will have varying number of ... 10-3 moles of [Link] contains = # x 10-3 moles of cle
ionisable chlorine atoms which is represented as below: ions.
+ + Compound i++ No. of ionisable chlorine atoms ... # x 10-3 = 3 x io-3
Therefore,thereare3molesofreplaceableCl®inthecompound.
Cocl`.6NH` 3
So, Crc13.6H20 is represented as [Cr(H20)6]C13.
Cocli.5NHi 2
COC13.4NHi 1

CoC13.3NHi Nil
Which of the following complexes (in solution) will have greater
In modem terms the complex ions are shown in square brackets value of molar conductivity? Explain giving reason.
with ionisable ligands outside the coordination sphere. The a. K4[Fe(CN)6] and K3[Fe(CN)6]
primary valencies are ionic bonds whereas secondary valencies b. [PtoJH3)2C12] and [PtQIT13)6]C14
are coordinate bonds. Thus the above complex can be rewritten
in modem terms as below: sdl.` .
y MQder`n. :\
wemet - `;A;,`:,:;* 'o:,caffi®n- \ Anion 1bta' a. On ionisation, K4[Fe(CN)6] gives
f¢r"la`
! x--s 8

form«la no.+ofions + K4[Fe(CN)6] - 4K® + [Fe(CN)6]4-

\ , -a <*r^,`=; siv - `
five ions
Whereas K3[Fe(CN)6] on ionisation gives
CoC13.6NH3 [C0qu3)6]C[3 [coorH3)6]3+ 3Cle 4
K3[Fe(CN)6] + 3K® + [Fe(CN)6]3-
CoC13.5NH3 [CoquH3)5Cl]C12 [C00JH3)5C1]2+ 2Cl® 3
four ions
CoC13.4NH3 [coon3)4ci2]cl [CO0VH3)4C[2]® cle 2
Since K4[Fe(CN)6] gives more number of ions (i.e. five ions)
CoC13.3NH3 [C0qu3)3C[3] Non-electrolyte - I zero as compared to K3[Fe(CN)6], (i.e. four ions) on ionisation,
K4[Fe(CN)6] will have greater value of molar conductivity.
7.6.2 FAILURE OF WERNER'S THEORY b. [Pt(NH3)2C12] is a non-electrolyte, it does not ionise in
Wemerwasthefirsttodescribethebondingfeaturesincoordination solution whereas [Pt(NH3)6]C14 ionises to give
compounds. But his theory could not answer basic questions like:
i. Why only certain elements possess the remarkable property [ptavH3)6]ci4 - [pto¢H3)6]4+ + 4 ci©
of forming coordination compounds? five ions

ii. Why the bonds in coordination compounds have direction Hence [Pt(NH3)6]C14 will have greater molar conductivity
as compared to [Pt(NH3)2C12].
properties?
iii. Why coordination compounds have characteristic magnetic
and op`tical properties?
Many approaches have been put forth to explain the nature Arrangethefollowinginorderofincreasingmolarconductivity:
of bonding in coordination compounds viz. valence theory a. K[cooqH3)2oro2)4]
(VBT), crystal field theory (CFT), ligand field theory (LFT) and b. [crqu3)3oro2)3]
molecular orbital theory (MOT). However, we shall be restricting
c. [cro¢H3)5INo2)]3 [cooro2)6]2
ourselves to VBT and CFT only.
d. Mg[COOu3) 0¢°2)5]

Sch In aqueous solution

From the experimental facts given below determine the correct a. K[Co0VH3)20J02)4]
structure of solid Crc13.6H20. Solution containing 0.2665 g of
Crc13.6H20 was passed through ration exchange resin in acid on ionisation [K®+[cOovH3)2oro2)4]e
form. The acid liberated was found to react completely with 30 2 ions; charge = +I or -1
mLofo.10MNadH.(Molecularmassofcrc13.6H20=266.5) b. [Cr(NH3)3(N02)3] being non-electrolyte, does not ionise.
a.0 b.1 a.2 d.3 c. [crovH3)5oro2)]3 [coovo2)6]2

ifiHun [Link]=¥=10-3moles on ionisation 3 [crorH3)5oro2)]2+ + 2[coquo2)6]3-

30 mL x 0.10 M -3 x lo-3 5 ions; charge = +6 or nd

Moles of NaoH =
1000 mL d. Mg[CrovH3)OV02)5]

Moles of NaoH = Moles of HC| = 3 x |o-3

on ionisation
Let 1 mole of compound contains # moles of replaceable Cle Mg2++[Cr3+OJH3)OVO-i)5]-2
ions.
2 ions; change = +2 or -2
 Coordination compounds 7.25

Greater the number of ions and greater the total ®ositive or But in aqueous solution, the above order of mobilities is
negative) charge produced after ionisation, greater is the value of reversed, because hydration oc charge density oc mobilities.
molar conductivity. Hence, increasing order of molar conductivity So Li© ion is extensively hydrated than Cs© ion and hence
is b = a < d < c. the mobilities and conductance of the above compounds is
in the order d > c > b > a.

Amangethefollowinginorderofdecreasingmolarcondrctivity 7.7 SIDGWICK'S ELECTRONIC

in aqueous solution:
CONCEPT OF COORDINATE BOND
a. Li[coorH3)2INo2)4]
In 1927, Sidgwick introduced the concept of coordinate bond,
b< Na[C0qu3)2qu02)4]
which is also sometimes called polar or dative bond. According
C. K[C0qu3)2(N°2)4] to Sidgwick, a ligand donates an electron pair to the central metal
d. CS[CoquH3)2 qu°2)4] ion and thus a coordinate bond is fomed, which is designated
as LiM. This concept is based on the fact that all the ligands
S. .`.:. The above mentioned complexes ionises as follows: contain at least one lone pair of electrons.

a. Li[CoorH3)20J02)4] - Li:aq) + [C0quH3)20V02)4]8q) 7.7.1 SIDGWICI{'S EFFECTIVE ATOMIC NUMBER

(EAN) RULE
b. Na[CoOJH3)20ro2)4]+ NaSq)+ [CO0JH3)20J02)4]8q)
On the basis of his concept of coordinate bond, Sidgwick
c. K[coorH3)2ovo2)4] -K:aq)+ [coo{H3)2ovo2)4]g® suggested that central metal ion will continue accepting electron
pairs from the ligands till the total number of electron surrounding
d. CS[CO(NH3)2 0to2)4]-CS:aq) + [C00VH3)20V°2)4]8q)
the metal ion including those donated by the ligands is equal to
In all the cases, the number of ionic species produced are that of next noble gas. The total number of electrons is called
same (two in each case), the number of charges produced Effective Atomic Number and the rule is known as Effective
are same (+1 or -1 ). Molar conductivity depends directly on Atomic Number (EAN) rule.
the mobility or movement of species produced on ionisation. Effective atomic number of central atom/ion in the complex
Mobility of ions oc charge density. can be calculated as follows:
Since the charge density (ion-ic charge/ionic radius) EAN - Z - Jr + y
decreases and hence the mobilities of ions should be in the Z = Atomic number of central atom/ion
order as: jx= Oxidation state of central atom/ion
Li© > Na© > K© > Cs© y= No. of electrons gained by LiM coordination

Table 7.12 Complexes whose central atom/ion obeys FAN rule

+\\Atomic number Of neut`+i
complex Centralatom •;Atomic , Oxidation state Electrons gained ` J EAN'` r

lwmber y : p ,cegivra ` atom

`JJ(
bycoQrdinatlEN,', (g,I-#:+)# : / + highernoblegas+ +
(Z) (y'
[Fe(CN)6]4- Fe 26 +2 2 x 6 -12 26 -2 + 12 = 36 Kr = 36

[Cu(CN)4]3- Cu 29 +1 2x4-8 29 - 1 + 8 = 36 RT = 36

[pdo¢H3,6]4+ Pd 46 +4 2 x 6 -12 46 -4 + 12 = 54 Xe - 54
[pdcl4]2- .Pd 46 +2 2x4-8 46 - 2 + 8 = 54 Xe - 54
[ptquH3,4,2+ Pt 78 +2 2x4-8 78 -2 + 8 = 84 Rn = 86

[Cr(CO)6] Cr 24 0 2 x 6-12 24 -o' + 12 -36 Kr - 36

[Fe(CO)5] Fe 26 0 2 x 5 -10 26 -0 + 10 = 36 Kr - 36
INi(CO)4] Ni 28 0 2x4-8 28 -0 + 8 - 36 Kr - 36

FAN rule has some usefulness, that is, it predicts the number of ligands in many complexes. It has, however, only of qualitative
significance, because there are many other complexes which are known to be very stable, but do not obey BAN rule, as shown in
Table 7.13 .
7.26 Inorganic chemistry

Table 7.13 Complex whose central atom does not obeys EAN rule

i::;J;3\-:+>:;; ( Cpmptex - erttra at®" + atomic numbe` oxidatiotn stina` ,`y ':, ++ ++ Electrons gained :i§&#xA*\!r
+ coordination (
(xp i:r -

[Fe(CN)6]3~ Fe 26 +3 2 x 6 -12 26 -3 + 12 = 35
[CrquH3)6]3+ Cr 24 +3 2 x 6-12 24 -3 + 12 = 33
INiorH3>6]2+ Ni 28 +2 2 x 6 - 12 28 ~ 2 + 12 = 38
Ni 28 +2 *2 x 3 x 2 = 12 28 ~ 2 + 12 = 38
INi(en,3,2+
[Mn(H20)6]2+ Mn 25 +2 2 x 6 -12 25 -2 + 12 = 35
[CO(CN)6]4- Co 27 +2 2 x 6 - 12 27 -2 + 12 = 37
[CuO{H3)4]2+ Cu 29 +2 2x4-8 29 -2 + 8 = 35
INi,CN)4]2- Ni 28 +2 2x4=8 28 - 2 + 8 = 34
*Note: (en) is bidentate ligand

7.7.2 AppLlcATIONs OF FAN RULE illHHme

1. It predicts the number ofunpaired electrons in the complex a. In [Mo(CO)x], EAN of Mo = 54
and hence magnetic moment. Z of Mo = 42
2. It predicts the molecular formula of simple carbonyl. 0xidation state of Mo is zero
No. of electrons donated by x CO groups = 2x
BAN of Mo in [Mo(CO)ur]
Calculate the BAN of the underlined atoms in the following 42 - 0 + 2x = 54
complexes.
a. [Ca(edia)]2-
... J¥-4±
2
-6
b. INi toy} (en) orH3)3]2+ x-6
-`'` S..;` Formula is [Mo(CO)6].
b. [C02(CO)I;
a. [Ca(edta)]2-:
Atomic number (Z) of Co = 27
(Z of Ca = 20) 0xidation state of Co = 0
Let oxidation state of Ca be x,
In [Co2(CO)x], i.e. one electron is shared with other
I.. x+ 1 x (i)--2 Co atom due to Co{o bond, which means contribution
= JX-+2 coming because of Co~Co bond is 1.

Coordination number of (edta) = 6. For EAN of each Co = 36,

( ... edta4- is hexadentate ligand) 27-o+,+¥-36

... EAN of ca = (20 -2) + 2 x 6 = 30
=x-8
So, BAN rule is not valid.
Formula is C02(CO)8
b. INi ®y) (en) Oun3)3]2+
c. Hxcr(CO)5
Ni (Z-28); `
Atomic number (Z) of Cr = 24
Let oxidation state of Ni be :I,
Electrons gained by 5 CO groups .= 2 x 5 = 10
.'. J¥ + 0 + 0 + 3 x 0 - 2
= x-+2 EAN of cr = 36 = 24 + 10 + x

[Pyridine, (py); and ammonia, (NH3) are monoden-tate > x = 36 -24 -10 = 2
ligand whereas ethylenediamine (en) is bidentate ligand] i.e, formula is H2Cr(CO)5.
So, EAN of Ni = (28 -2) + 2 + 2 + 2 x 3 = 38 d. HxCo(CO)4
So, BAN rule is not valid. Atomic number (Z) of Co = 27
Electrons gained by Co due to 4 CO groups = 2 x 4 = 8
BAN of Co = 36 = 27 + 8 + x
the following compounds. 3 x= 36-27-8=1
b. [C02(CO)J i.e. formula is HCo(CO)4.
d. HxCO(CO)4 e. EAN=36 f. EAN=36
f. [Cr(C6H6)2]
Refer to Section 7.16.1@), Point 2, Figs. 7.50 and 7.51.
 Coordination compounds 7.27

b. 1st Method: Neutral metal c-count method:

2Mo = 42 x 2 = 84e-'s
Which of the following folio AN rule.
(Mo = Mo) = 2 ; 3 = 6e-'s
4(Single bonded halogens) = 1e-donor
- 4 x I - 4e_
2(Cyclopentadiene) = 2 x 5e-= log-
... BAN = 84 + 6 + 4 + 10 = 104 0Vot multiple of 18)
Hence does not follow BAN rule.
2nd Method: Oxidation state a-count method:
CICl

b. a+o-fB -1-I
CICl

CICI
CICI
a+b3-¥:LB
CICl

c. a+a+oB -I-I

2Mo+3 = 2(42 -3) = 39 x 2 = 78

CICl (Mo = Mo) bond = 2 x 3 = 6
4(Single bonded halogen) = Each halogen 2e- donor

d&Tlo(::,i'oB - 2 x 4 - 8e_
2(Cyclopentadienyl anion) = 2 x 4 = 8e-
2(Cyclopentadienyl anion) = 2 x 6 = 12e-
... BAN = 78 + 6 + 8 + 12 = 104 0Vot multiple of 18)
`:.: `` `` . ``

Hence does not follow BAN rule.

a. 1st method: Neutral metal e-count method.
c. Ist Method: Neutral metal a-count method:
2Mo = 42 x 2 = 84e-'s
2Mo = 42 x 2 = 84e-
(Mo - Mo) bond = 2e-'s
(Mo - Mo) bond = 2e-
(Bridging halogens) = Each halogen e- donor 4(Single bonded halogens) = 1e~ donor
= 3 x 4 (C1) = 12e-'s
- 4 x 1 - 4e_
2(Cyclopentadiene) = 2 x 5e-= 10
2(Cyclopentadiene) = 2 x 10 = log-
.., EAN = 84 + 2 + 12 + io = ng = 6 BAN = 84 + 2 + 4 + 10 = 100 0Vot multiple of 18).
18
Hence does not follow EAN rule.
EAN should be 18 or multiple 18. 2nd Method: Oxidation state c-count method:
Hence if follows EAN rule. -1-1
2nd Method: Oxidation state e-count method: Cl

e&MS,MOBe
-I

di::-
2(Mo+3) = (42 - 3) = 39 x 2 = 78

(Mo - Mo) bond = 2e-

4(Single bonded halogens) = 2e- donor
Mo+3 = (42 -2) = 39 - 4 x 2 - 8c_
2Mo+3 = 39 x 2 = 78e-'s 2(Cyclopentadienyl anion) = 2 x 6 = 12e-
(Mo - Mo) bond = 2e-'s ... FAN = 78 + 2 + 8 + 12 = 100 0{ot multiple of 18).
(Bridging halide) = Each halogen 4e- donor Hence does not follow BAN rule.
= 4 x 4 (Cl) = 16e-'s d. 1st Method: Neutral metal e-count method:
2(Cylopentadienyl anion) = 2 x 6e-= 12e-'s 2Mo = 42 x 2 = 84e-

... EAN = 78 + 2 + 16 + 12 = ± = 6 (Mo - Mo) bond = 2e-

18 2(Bridging halogens) = Each halogen 3e-donor
Hence it follows EAN rule. - 3 x 2 - 6e_
7.28 Inorganic chemistry

2(Single bonded halogens) = Each halogen 4e- donor outside the coordination sphere. This type of isomerism
- 1 x 2 - 2e_ occurs when the counter ion in a coordination compound
is itself a potential 1igand, e.g.
2(Cyclopentadiene) = 2 x 5 = 10e-
A. [CoBrovH3)5]S04 and [COO{H3)5 (S04)I Br
... EAN = 84 + 2 + 6 + 2 + 10 = 104 0Vot multiple of 18).
8. [codro3) (N113)5]so4 and [cO(NH3)5 (so4)] No3
Hence does not follow EAN rule.
C. [Ptc12(NI13)4]Br2 and [PtBr20VH3)4] C12
2nd Method: Oxidation state e-count method:

edyei`:'B D. [Crl2avH3)4]Br and [CrBrl(N113)4]I

a. Qualitative analysis: Ionisation isomers can be
distinguished by qualitative analysis. In aqueous
medium they ionise to form different ions in solution,
Cl-1 cF e.g. [CoBro{H3)5]S04 (A) and [CO0VH3)5(S04)]Br

2(Mo+3) = 2(42 -3) = 39 x 2 = 78e-'s (B)(A)givesawhiteprecipitateofBas04whentreated

with Bac12, whereas (8) does not give any reaction.
(Mo - Mo) bond = 2e-
[COBrovH3)5]S04 -[CoBrovH3)5](2a:) + SOS(=q)
2(Single bonded halogens) = Each halogen 2e~ donor
- 2 x 2 - 4e_ Sofrady+Bac12(so[n)-Bas04J+2C1%
2(Bridging halogens) = Each halogen 4e- donor White ppt

- 2 x 4 - 8e_ This indicates that S042- is present outside the

coordination sphere.
2(Cyclopentadienyl anion) = 2 x 6 = 12e-
b. Witll AgN03 soluion: (A) does not react with AgN03
... EAN = 78 + 2 + 4 + 8 + 12 = 104 0Vot multiple of 18).
soluion but (8) gives pale yellow precipitate. This
Hence does not follow BAN rule.
indicates that Br° is present outside the coordination
sphere in (11).
7.8 lsoMERISM IN COORDINATION
[C00VH3)5(S04)]Br-[CO0VH3)5(S04)](:q)+Br8q)
COMPOUNDS
Complexes which have the same molecular or ionic formula, i.e. ABN03(soh)+Br:q)-AgBrJ+N08
same chemical composition, but differ in structural arrangement Pale yellow ppt.
of their atoms are called isomers. These isomers have different c. Conductance method: In aqueous medium, ionisation
properties. The phenomenon that gives rise to, different isomers isomers ionise to give charged species. Greater is the
is called isomerism. number of ions ®articles) or charges produced, greater
Coordination compounds exhibit two main type of isomerism is the conductance, e.g.
A. Structural isomerism [CoBrovH3)5]S04 (C) and [CO0VH3)5 S04]Br (D)
8. Stereoisomerism
(C) ionises to give
[CoBro{H3)5]2+ + SOZ-
[CoBrovH3)5]S04 -
two ions
i.e. two ions (or particles) and 4 charges (+2 and -2)

(D) ionises to give

[CO0JH3)5S04]Br+[Co0VH3)5S04]©+Bra
two ions
i.e. two ions (or particles) and 2 charges (+I and -1)
Since in (C) and (D), number of ions produced are same
but (C) has more charges than (D). Thus (C) has more
conductivity as compared to (D).
2. Hydrate or solvent isomerism: This type of isomerism is
7.8.1 STRUCTURAL ISOMERISM [Link](H20)canbepresent
This isomerism arises in those complexes which have same in the complex in two ways:
molecular formula or chemical composition, but differ in i. as a ligand, i.e. as a part of coordination entity.
structural or atom to atom bonding sequence. ii. as water of crystallisation, i.e. outside the coordination
Structural isomerism is of the following types: entity.
I. Ionisation isomerism: Complexes which have the same Hydrate isomers are obtained when H20 molecule
empirical formula but give differeht ions in solution or present as water of crystallisation are exchanged by the
ionisation are called ionisation isomers and the phenomenon coordinated groups or ligand present in the coordination
is called ionisation isomerism. It arises due to interchange entity. Hydrate isomers have different physical and
of ligands in the coordination sphere and the ions present chemical properties.
 Coordination compounds 7.29

For example, Crc13.6H20 exists in three different Distinction between coordination isomers:-
isomeric forms : i. Electrolysis methods: Coordination isomers can be
Isomers Colour distinguished by electrolysis of an aqueous solution.
a. [Crc13(H20)3].3H20 In example (a) above, in first case cobalt complex
b. [Crc12(H20)4]Cl.2H20 Green migrates towards the negative electrode (anode)

C. [Crcl(H20)5]C12.H20 Bluish green ( ... Co complex is positively charged) and Co complex

will be deposited at anode.
d. [Cr(H20)6]C13 Violet
Apart from their colours, the three isomers can be Cr will be deposited at positive electrode (cathode)
distinguish by quantitative method by reaction with since the Cr complex is negatively charged. Reverse
AgN03 in aqueous medium. will happen in its coordination isomer.
ii. Conductivity method: In example (c), the former
a. [Crc13(H20)3].3H20 H:+ [Crc13(H20)3](aq) isomer is (+3, -3) electrolyte and latter is (+1, -1)
No precipitation of Agcl. electrolyte), thus conductivity of the former isomer is
b. [Crc12(H20)4]Cl.2H20 greater than that of latter.
21^

[Crc12(H20)4]?a®+CL?aq) iii. These isomers can also be distinguished by X-ray

diffraction and IR (infrared) spectroscopic method.
C1%®+Ag®-AgcIJ
4. Linkage isomerism: This type of isomerism is shown
c. [Crcl(H20)5]C12.H20
-[Crcl(H20)5]2++2Cl?aq) :ibt,hd°esn:a:e°:£rgda£:da,tfe°.:.,C;%£;:%d#%££S,C;2n6:2inetac:
2C,9ady+2Ag®-2Agc,J When an ambidentate ligand, having two different donor
atoms coordinates to the central atom through either of its
d. [Cr(H20)6]C13-[Cr(H20)6]::q)+ 3C1%® two donor atoms, two different complexes are obtained,
3Cl?a®+3Ag©-3AgcIJ and they are known as linkage isomers, the phenomenon is
known as linkage isomerism.
With AgN03, the three isomers (a), a) and (c) give
For example, [CO0VH3)50V02)]C12 and
a white precipitate of Agcl in the molar ratio of
[CoO`ur3)5(ONO)][Link]
;:i:o:ersesopfe:t,[8e][oy;:nodj:s:t::gt£:ecporoersde£:Ca:;::]s'p2h::e: becausetheyhavedifferentstructures.[Co(NH3)5(N02)]Cl
is yellow in colour, whereas [Co(NH3)5(ONO)]C12 is red in
These isomers can also be distinguished by conductivity
measurement method, which will give different colour.

number of ionic species. The two linkage isomers are named as:
-s.\No.
No. af .,ionicspeeiea\\ • Charges;.- ;es;>^;J^:,ee, [C O (NH3 )5 (N02)] C 12 pentaamminenitrito-N-cobalt(Ill)
chloride

[CO(NH3)5(ONO)]C12pentaamminenitrito-O-cobalt(Ill)
a, [Crc13qu20)3].3H20 1 0 chloride
b. [Crc12(H20)4]C1.2H20 2 2(+1 and-I) These isomers can be distinguished by UV, IR, NMR
C. 3 4(+2 and -2) spectroscopic and X-ray diffraction methods.
[Crcl(H20)5]C12.H20
5. Polymerisation isomerism: This type of isomerism exists
d. [Cr(H20)6]C13 4 6(+3 and -3)
among those complexes, which have the same empirical
Since the number of ionic species produced is increasing formula but each of the isomer is some simple multiple of
in the order a < b < c < d, thus molar conductivity also the empirical formula, e.g.,
increases in the same order i.e., a < b < c < d. Pt :NH3 :Cl
3. Coordination isomers: This isomerism is shown by those
a. i. [Ptc12QVH3)2] 1 : 2 :2
complexes which are composed of complex cation and
complex anion. It arises due to interchange of ligands ii. [Pt(NH3)4][Ptc14] 2 : 4 :4 or [Link]

between the cationic and anionic complex entities. Some iii. [Pt(NH3)3C1]i[Ptc14] 3 : 6 :6 orl:2:2
of the examples are as follows: Co :NH3 : N02
a. [CoOVH3)6] [Cr(CN)6] is isomeric with
b. i. [C00VH3)30V02)3] 1 : 3 :3
[Cro{H3)6] [CO(CN)6]
ii. [C00VH3)6] [CO0V02)6] 2 : 6 :6 or 1: 3: 3
b. [Cu(NH3)4] [Ptc14] is isomeric with

[PtovH3)4] [CuC14] [cOoJH3)5 oro2)]3 [coavo2)6]2

C. [CrovH3)6] [Cr(SCN)6] is isomeric with
5 : 15 :15or [Link]
[CrovH3)4 (SCN)2] [CrovH3)2 (SCN)4]
These isomers can be distinguished by mass spectro-
In these pairs the central metal atom in the two
scopic methods.
coordination spheres may be same or different.
7.30 Inorganic chemistry

6. Coordination position isomerism: This type of isomerism

is shown in polynuclear complexes. This isomerism arises
due to interchange of ligands between the coordination Describe a simple test to distinguish between the following
sphere of various central metal ion. Coordination position pairs of compounds:
isomerism is thus a special type of coordination isomerism. i. (A) [Co(N113)5Br] S04 and (B) [CoquH3)5 SQ4] Br
ii. (A) [Cr(H20)6]C13 and (8) [Cr(H20)5 Cl] C12.H20

a[:rHe3X)::oP[{::>coquH3)2ci]S04(Unsyrmetnca]) iii. (A) cz.s [Ptc12Q¢H3)2] and {8) frczRE [Ptc120{H3)2]

iv. (A) and (a) Two enantiomers of [Co(en)2C12]®
[Link](III)-di-H-hydroxodiamminechlorido V. (A) [Cr(NH3)6] [Cr(N02)6] and
cobalt(III)sulphate
@) [CrovH3)4 0V02)2] [Cr(NHS)2 qu02)4]
vi. (A) [ptorH3)2cl2] and (8) [ptquH3)6]cl2
and[clorH3)3cO<::>coorH3)3c]so4(sy-ethcal)
vii. (A) [CoorH3)5Cl]So4 and (8) [CoquH3)5 So4] C1
triamminechloridoocobalt(III)-di-LL-hydroxotriamm-
inechloridocobalt(Ill) sulphate
sol
i. (A) and (8) are distinguished by qualitative method. (A)
b.i.[quH3)4co<NOH22>coorH3)2ci2]ci2i¥¥:rthcaL giveswhiteprecipitateofBas04withBac12solutiondueto
thepresenceofS042-ascounterion.(8)givespaleyellow
tetraamminecobalt(III)-H-amido-pr-peroxodiammine
ir;#£3t:toeLu:Lfo£3::t(oP:hlfeL:LrLeyses:;:boLfBL:oTOHn4a°s¥!u:ite:
dichloridocobalt(Ill) chloride
ion.
ii. (A) and (8) are distinguished by conductance method. (A)
££.FH3)3CICO'`NOH2>CoorH3)3C]C12!;¥ys¥c:I;a:a[
gives 4 ions with high charge whereas (8) gives 3 ions with
low charge in aqueous solution as shown.
triamminechloridocobalt(Ill)-pr-amido-H-peroxdtriam-
minechloridocobalt(III) chloride
or LL-amido-pr-peroxobis(triamminechloridocobalt(III)
A- [Cr(H20)6]3++3C|°
4 ions (+3 and -3) charge
chloride
7. Ligand isomerism: This type of isomerism arises because of
the ligands, which are present in their isomeric forms, e.g.
8- [Cr(H20)5Cl]2++2cie
4 ions (+2 and -2) charge

So, conductance of (A) will be higher than that of 8.

fH2-CH+H3I fH2-CH2iH2 Further (A) and (8) are also distinguished by quantitative
NH2
\/ NH2

1,2-diaminepropane
H2ry
\/
I,3-diaminepropane
pr2
method, withAgN03 (A) and (8) gives a white precipitate

t°hfeAp::s]e:nc:hoef¥:La:;a£:I:::i%]r8Sapse::I::::ii::::ating
®n) (tn) iii. (A) C!.S [Ptc12(NH3)2] has some value of dipole moment
Both are bidentate and neutral ligands. When these are while the (8) fr¢# [Ptc12(N113)2] has zero value for its dipole
c6ordinated to the metal atom, two isomers are obtained. moment.
These are called ligand isomers and the phenomenon is
[Link][Co(en)2C12]©isdextrorotatory(d-fom)
called ligand isomerism.
and the other enantiomer is levorotatory (/-form)
For example, [Co(Pn)2C12]© and [CO(tn)2C12]©
v. The given isomers can be distinguished by conductivity
H3q.,, Cl measurement, (A) conducts as (3+, 3-) electrolyte while
(8) conducts as (I+,1-) electrolyte.
HC
(A) - [CroJH3)6]3+ + [Cro¢02)6]3-

H2C :ii!c:o'€I:
H2 ci H2
(3+, 3-) electrolyte

(8)-[CroJH3)40V02)2]©+[CrovH3)20V02)4]°
I

(I+,` I-) electrolyte

Thus (A) has higher value of molar conductance than (8).
vi. (A) and (8) can be distinguished by conductance method.
-J=T-cH2

iiE1
\/ The ionisation of the given complex compounds can be
shown as
(A) - No ions
H2'c-Hr-:1---¥2-cH2 I

G)- [Pto{H3)6]3++2C
three ions
 Coordination compounds 7.31

Therefore (A) has zero value of its electrolytic conductance [Link] Geometrical Isomerism in Complexes with
whereas (8) gives 3 ions, it has some value of electrolytic C.N. 2 and 3
conductance. Geometrical isomerism is not found in complex compounds with
vii. (A) and (8) are distinguished by qualitative method. (A) coordination number 2 and 3 , since in these cases all the positions
gives white precipitate of Bas04 with Bac12 solution due occupied by the ligands round the central metal atom are adjacent
to presence of S042- ion as counter ion. (8) gives white to one another.

g:;uct±£:I:aj:Cot:fh:CpLre(sse°n]:eb:ef:=©|:n4:sHc)ouwntttehr)%:T°3 [Link] Geometrical lsomerism in Tetrahedral

Complexes (C.N. = 4)
Geometrical isomerism cannot be shown by tetrahedral complexes,
isomers of the and also give increasing since all the four ligands in this geometry have adjacent position
order of the conductance of the isomers. (i.e., cz.5 position) to one another and all the four bond angles are
the same.(= log.5o).
a. [Cr(H20)6]Br3 b. [Cu(H20)4]C12
``

[Link] Geometrical Isomerism in Square Planner

a. Hydrate isomers of [Cr(H20)6]Br3 are: Complexes (C.N. = 4)
i. (A) [Cr(H20)6]Br3 Beforediscussingtheg9ometricalisomerismexhibitedbyvarious
ii. (B) [Cr(H20)5Br]Br2.H20 types of square planar complexes, we should know how cz.s and
fra#s isomers of a square planar complex are named. A square
iii. (C) [Cr(H20)4Br2]Br.2H20
planar complex having similar ligands at adjacent positions (90°
iv. (D) [Cr(H20)3Br3].3H20
apart) is called cz's-isomer while a square planar complex having
0n ionisation the above hydrate isomers give two similar ligands at opposite positions (180° apart) is called
i. (A) + [Cr(H20)6]3++3Br°(4ions) ` frtz#s-isomer. Thus a square planar complex having two similar
ii. (8)+ [Cr(H20)5Br]2+ + 2Br©+ H20 (3 ions) ligands at 1 -2, 2-3, 3-4 and 1 -4 positions is called cg.s-isomer, while

iii. (C) + [Cr.(H20)4Br2]® + Br© + 2H20 (2 ions) that having two similar ligands at 1-3 and 2-4 positions is called
frcz72s-isomer, c;.s-and f7~¢J7s-isomer.s are also named by numbering
iv. (D) No ions are formed.
[Link][Pd2+C12Br]2-iftwoC1°[Link]
Greater the number of ions formed, greater is the
other or at 1-2 positions, it is named as cz.s-dichloro bromoiodo
conductance. Hence, increasing order of conductance
palladium (11) ion or I ,2-dichloro bromoiodo palladium (11) ion.
is D<C<B<A
Ontheotherhand,iftwoC1°ionsareplacedfro7!stoeachotheror
b. Hydrate isomers of [Cu(H20)4]C12 are at I -3 positions, it is named as trams-dichlorobromoiodo palladium
i. (A) [Cu(H20)3Cl]Cl.H20 (11) ion or 1, 3-dichlrobromoiodopalladium (11) ion (Fig. 7.1).
ii. (B) [Cu(H20)2C12].2H20 (4) (I)

iii. (C) [Cu(H20)4]Ct2 BrC1

0n ionisation, the above hydrate isomers give

i. (A) -[Cu(H20)3Cl]®+Cl© (2 ions)
ii. (B)-Noions (3) (2) (3) ' (2)

iii. (C) -[Cu(H20)4]2++ 2Cl© (3 ions)

(a) cis-dichloro bromoiodo (t)) trams-dichloro bromoiodo
palladium (11) ion or palladium (11) ion or 1, 3-dichloro
Greater the number of ions formed, greater is the
I, 2-dichloro bromoiodo palladium bromoiodo palladium (11) ion,
conductance. Hence order of conductance is 8 < A < C.
(11) ion, [Pd2+C12Br|]2- [Pd2+C|2Br|]2-

7.8.2 GEOMETRICAL ISOIVIERISM

Fig. 7.1 Nomenclat:r:qoufa::OpTaentan;C::#,Se:.nd trams) isomers Of
The complex compounds which have the same ligands in the
coordination sphere but the relative position of the ligands round
Here we' shall consider geometrical isomerism in square planar
the central metal atom is different are called geometrical isomers
complexes of [Ma4], [Ma3b], [Mab3], [Ma2b3], [Ma2bc], [Mabcd]
and the phenomenon is called geometrical isomerism.
and [M(AB)2] type in which M is the central metal atom; a, b, c
In a given complex compound the two ligands may occupy
and d are monodentate ligands and (AB) is an unsymmetrical
positions either adjacent to each other or opposite to each other. bidentate ligand, since it has two different dbnor atoms namely A
The complex compound having two ligands occupying the
and 8.
adjacent positions to each other is called cis-isomer while that in
which the two ligands occupy opposite positions is called trans- 1. Square planar complexes of [Ma4], [Ma2b] and [Mab3]
isomer. Hence geometrical isomerism is also called cid-fr¢7?a type: Square planar complexes of this type do not show
isomerism. geometrical isomerism, since all the possible spatial
Geometrical isomers of a complex differ in physieal arrangement of four ligands round the central metal atom
characteristics such as dipole moment and visible/uv spectra. is the same.
 7.32 Inorganic chemistry

2. Square planar complexes of [Ma2b2] type. Important which has N and 0 atoms as its donor atoms (i.e., A = N
examples of square planar complexes of this type are and 8 -0).
[Pt(NH3)2(C12)]°9 [Pt(Py)2C12]°, [PdovH3)2(N02)2]° etc. [Cu2+(gly)2]]°isalsoanexampleofsquareplanarcomplex
These complexes exist in cis- and trams-isomers. These of [M(AA)2] type. This complex also exhibits c!.a-/rcz#s
isomers of [Pt2+(NH3)2Br2]° are shown in Fig. 7.2. In (a) isomerism.
sincebothNH3moleculesandbothBr°[Link]
other, it is called cis-isomer. On the other hand, in (b) since [Link] Geometrical lsomerism in 6-coordinated
bothNH3moleculesandbothC1°ionsarefr##swithrespect Complexes: Octahedral Complexes
to each other, it is called trams-isomer. We know that a complex compound having central atom with
Br NH3 Br NH3 coordination number equal to 6 is octahedral in shape. Before
discussing the geometrical isomerism exhibited by various types of
octahedral complexes, we should know how cz's- and frcz#is-isomers
\,,;H3 H3N of an octahedral complex are named. In an octahedral complex, if
two similar ligands are placed on any of the twelve edges of the
(a) cis-isomer (b) trams-isomer
octahedron, they are said to be in cz.a position. On the other hand,
Fig. 7.2 tis-and trams-isomers of [Pt2+(NH3)2Br2]° •if two similar ligands are lying on a straight line which passes

3. Square planar complexes of [Mabcd] type. Square planar through the center (where the metal ion is placed),
complexes of this type exist in three isomeric forms. For H2H2
example, [Pt2+(NH3)@y)(Cl)(Br)] exists in three isomeric H2C-N N-CH2 NN
forms shown below in Fig. 7.3. These isomeric forms can be •EIEIIE
obtainedbyselectingoneligand,sayNH3,andthenplacing
the remaining three legands, one by one f7.¢#J to NH3.
NH;,`_i:-j7 Py NH;,,`-;;-j7 Py NH:,,i-ii Br

H2C O-C-O
c:i/Z<-::-i;Br Br/;Z<-::-*C:i C:1`t<-::*p;:/
Fig. 7.3 Three isomen.c forms of [Pt2+(NH3) (py) (CL) (Br)I

[pt2+ovo2)ty)orH3)ovH2oH)]+and[pt2+(c2H4)ovH3)(cl)
Br] are other examples of square planar complexes which /r¢#s-isomer

exist in three isomeric forms. fig. 7.5 cts-and trans-isomers of [Pt2+(gly)2]

The existence of three isomeric forms in case of the they are said to be in frczus position. Thus in an octahedral complex,
complexes mentioned above indicates that these complexes the two ligands at positions 1-6, 2-4 and 3-5 are frcz#s to each
have square planar geometry. other and the two ligands occupying. positions 1-2, 1-3, 6-4 etc.
4. Square planar complexes of [Ma2bc] type. [Link] planar are cz.s to each other.
complexes of this type also show cz.a-/r¢#s isomerism. For
example,[Pd2+C12Brl]2-ionexistsinc!.s-andfrm!#s-isomers
as shown below in figure.

Br
•,'\i+;
OR 4`,i=-f:-i,-,.2
#______\ Cl
cj.s-isomer fra#s-i somer FjgJ.6cNoummp?:r:ogu:fdstj#e"cgeanntdr:LfEL:t:eL9f:Lna,r#:ahedraL

Fi.g. 7.4 cis-and trans-isomers of [Pd2+C12Brl]2-ion

The numbering system of ligands shown in Fig. 7.6 can be
[Pt2+@y)2(NH3)Cl]- is another example of square planar exemplified by considering the nomenclature of cz.a- and /rcz#ig-
complex of [Ma2bc] type which exists in cz.s- and tr¢#s-
isomersof[Co3+(NH3)4C12]+ionwhichisanoctahedralcomplex
isomers.
ion. Cis-isomer of this ion in which two Cl- ions are cz.s to each
5. Square planar complexes of [M(AB)2] type. Here M is other is also called i, 2-dichlorotetrammine cobalt (Ill) ion [See
the central metal ion and [AB] represents an unsymmetrical Fig. 7.7(a)]. Similarly, frcz#s-isomer of this ion in which two Cl-
bidentate ligand in which A and 8 are two different ions are trams to each other is also called 1, 6 dichlorotetrammine
coordinating (donor) atoms. Square planar complexes of cobalt (Ill) ion. [See Fig. 7.7(b)]
this type also exist in c!.s- and frcz#s-isomers. For example,
Here we shall discuss the geometrical isomerism in octahedral
[Pt2+(gly)2]existsincz.f-and/#¢#s-isomersasshowninFig. complexes of the following type:
Here gly represents the glycinato ligand, NH2.CH2COO-

jiunm I _IJ
 Coordination compounds 7.33

1. Octaliedral complexes of [Ma5] and [Ma5b] type: isomer. In this isomer two of the three cz groups and also
Octahedral complexes of this type do not show geometrical two of the three b groups are /rtz#s to each other (See
isomerism. Fig. 7.8). Hence this isomer is also called trams isomer.
2. Octahedral complexes of [Ma4b2] type: Important examples Examples: [Co(NH3)3C13], [CO(NH3)3(N02)3]."
ofoctahedralcomplexesofthistypeare[Co3+(NH3)4C12]+, [Cr(H20)3F3] [Cr(MH3)3C13] , [RhGry)3C13], [Ru(H20)3C13],
[Co3+(N113)4(N02)2]+[Link].a-and [Ir(H20)3C13], [Pt(NH3)3Br3]+, [Pt(NH3)313]+ etc. are
important examples of octahedral complexes of Ma3b3
:rh"o";-n£S]:mFefrgs..#S[:i::a:::Sm°efr[:°o3+BTOH£3!:?ro2::u£:;;;: type. Cis-(fac) and frcz73s-(mer) isomers of [CO(NH3)3Br3]
adjacent (i.e.,I and 2) positions of the octahedron while in are given in Fig. 7.9.
fr¢7?s-isomers these ions have the opposite (i.e., 1 and 6) Br
positions. Cz.s-isomer of [Co3+(NH3)4Br2]® ion is );e#ow-
brow# while frcz#s-form is }7e//ow in colour.
(a) ci's-isomer, (1, 2-dishlorotetrammine Cobalt (Ill) ion),
(yellow-brown)
rH3N
(b) Trans-isomer ( 1, 6-dishlorotetrammines cobalt (Ill) ion),
(yellow)
(a) cl's (or fac) isomer (b) frcz#s (or mer) isomer

fig. 7.9 tis (fac) and trams (mer) isomers of [Co(NHS)3Br3]

octahedraL complex

[Co(NH2CH2COO)3]a!sohastwogeometricalisomers,viz.,
facial and meridional (See Fig. 7.10). In the given complex
N and 0 atoms are the donor atoms.

(a) c!.s-isomer (b) Jrtz#s-isomer

( l ,2-dibromo rtetrammine ( 1 -6 dibromoroterammine
cobalt (Ill) ion). (yellow-brown) cobalt (Ill) ion). (yellow)

Fig. 7.7 cis-and trams-isomers of [Co3+(NHS)4Br2]© ion

3. OctahedraL complexes of [Ma3b3] type: We know that

an octahedron has eight triangular faces and six comers
(vertices). Octahedral complexes of [Ma3b3] have two ty|)es
of geometrical isomers :
(i) Facial or fac isomer (ci.s-isomer): In this isomer the
0\ /cH2
three a groups occupy the three comers (vertices) of
one triangular face while the other three b groups in o,c
this isomer take up the position of the remaining three Facialisomerof[Co0VH2CH2COO)3]°
vertices. This isomer is called facial or fac isomer. This
isomer is also called cz.s isomer, since the three a groups /cH<
O-C
are cz.s to each other. Similarly b groups are also cia to \o NH2
each other (See Fig. 7.8)
(I)
OR
/cH2
0 O-C-O 0
/
O-C
\ cH2/
NH2

Meridionalisomerof[Cooun2CH2COO)3]°
b`'b
(a) cl`s (or fac) isomer (b) Jra#f (or mer) isomer Fig. 7.10 Facial and merdional isomers of [Co(NH2CH2COO)3]°

fig.7.8tl.S-(Orfac)aoncdtdath?a:(Oc:##xisomers0fMa3b3type 4. Octahedral complexes of [Ma4bc] type: [Co3+OVH3)4(H20)

Br]2+ ion is an important example of octahedral complex
(ii) Meridional or mer-isomer (fro«s-isomer): In this of [Ma4bc] type. This ion has cz.a-and /rcz"s-isomers whose
isomer the three cr groups are in one plane and the other structures are given in Fig. 7.11. In cz.s-form two NH3
three a groups are in a perpendicular plane, a and b molecules have cz.s positions to each other and in trams-form
groups lie along the meridian of a sphere (imagine our these ligands (i.e. , two NH3 molecules) have fr¢#s positions
earth). Hence this isomer is [Link] meridional or mer with each other.
7.34 Inorganic chemistry

5. Octahedral complexes of [Ma2b2C2] type:

[Pt4+(NH3)2tyy)2Br2]2+ ion is an important example of
octahedral complex of [Ma2b2c2] type. This ion can exist
theoretically in five geometrical isomers that have been
shown in Fig. 7.12, but it is only three isomers that have
been actually isolated. It may be noted from the figure that
OH2 NH2 (I) form is a cz.s-form since in this form two identical ligands
(a) cJ.a-isomer a) Jrcz#s-isomer are occupying adjacent positions. Form (11) is frcz#s-form
because in it the two identical ligands are placed at opposite
Fig. 7.11 Structure of cis-and trams-isomers of [Co3+(NH3)4(H20)Br]2+
octahedral complex ion. positions.

NH3 Br
(I) (cz`s-isomer) (II) (fra#s-isomer)

fig. 7.12 All possible five geometrical isomers of [Pt4+(NH3)2(py)2Br2]2+ ion

6. Octahedral complexes of [Mabcdefl type: Octahedral complexes which have different monodentate ligands have been prepared
for Pt (IV), [Pt4+¢y) (NH3)(N02)(Cl)(Br)(I)] is the only complex of this type of complexes. Theoreticauy 15 geometrical isomers
are possible for this complex compound. In fact only three geometrical isomers have been isolated.
7. Octahedral complexes of M(AA)3 type: Octahedral complexes of this type of do not show geometrical isomers.
8. Octahedral complexes of [M(AA)2a2] type: Here (AA) represents a symmetrical bidentate ligand in which A and A are two
identical coordinating (donor) atoms, [Co(e#)`2C12]®, [CO(e#)2(NH3)2]3+, [CO(e#)2.(N03)2]©, [Cr(e#)2C12]©, [Cr(C204)2(H20)2]-.

!]nr:+,(rca2„?.4£)s2oci2::;.eACs.a:eetxhaeme;,:mc?s`_e:n°df,::t„ash.:sdor:ecr:::[[ecxo[3°+::„°):i#o)£¥r]e¥:;Ena[?nhF°£:th7e.S[e3:°mp]exIonsexistsinc!J-

OR

cz.a-isomer

OR

H2C-H2N NH2`dH2
Br

frcz7€s-isomer

Fig. 7.13 cis-and trans-isomers of [Co3+(en)2Br2]+ on

 Coordination compounds 7.35

Symmetrical/unsymmetrical natul.e of cz.s-and fra«s- 9. Octahedral complexes of [M(AA)2ab] type:

isomers: The structures of mirror images of cis-and Jr¢#s- [Co3+(e#)20{H3)C1]2+isanirnportantexampleofoctahedral
forms of [Co3+(e#)2Br2]+ ion are given at (a) and (b) of complex of [M(AA)2ab] type. This complex ion exists in cz.s-
Fig. 7.14 respectively. Since the structure ofcz.s-isomer and andtrcz#[Link].s-isomerthetwomonodentateligands
its mirror image are non-super imposable on each other, viz., NH3 and Cl-occupy the adjacent (i.e., cz's) positions
cz.a-isomer is unsymmetrical. On the other hand, since the while in Jr¢#s-isomer these ligands occupy opposite (i.e.,
structure of fr¢7!s-form and its mirror image are super- !ro7!s) position (See Fig. 7.15). [Ru3+(C304)2¢y)OV02)]2-
imposable on each other, /rcz7ts-isomer is symmetrical. Thus also exists in cz.s- and Jrcz#s-isomers.
cz.s-isomer is optically active but frcz77s-isomer is optically
inactive.

e„N

Mirror Mirror

(a) Stmcture of cis-isomer of [Co(en)2Br2]® a)Structureoftrans-isomerof[Co(en)2Br2]©ion

and its mirror image and its mirror image

Fig. 7.14 Structure of ci.s-and trams-forms of [Co(en)2Br2]® ion and their mirror images.

a! groups are cz.s to each other and the two a groups are
f7~a!#s to each other. Both these isomers have mirror
plane passing through the metal (M), AA and cz, cz/b,
b and hence these give only super imposable mirror
image. Both these isomers are symmetrical and hence
are optically active, i.e., archiral.
Examples: [Co3+(en)(NH3)2C12]+ and [Co3+(C204)
(NH3)2(N02)2]- are important examples of octahedral
cis-isomer frc7%s-i somer complex of [M(AA)CZ2b2].
Fig. 7.15 tis-and trams-isomers of [Co3+(en)2(NH3) (Br]2+ ion Geometrical isomers of [Co3+(en)(NH3)2Br2]+ ion. This
ion is an [Link] of [M(AA)a2b2] type. This ion has
As in case of [Co3+(en)2C12]© ion, the cz.s-isomer of
[Link] geometrical isomers.
[Co3+(en)2(NH)3(Cl)]2+ is also unsymmetrical while its
frcz#s-isomer is symmetrical. Thus cz.a-fom is optically t£,:a::colts::sr:a,:I;[]anr:;,i:;:ot::rBTg[¥a;:1::ed:[asroe:;:;:
active while fra!»s-isomer is optically inactive.
each other. [See Fig. 7.16]. This isomer is unsymmetrical
10. Octahedral complexes of [M(AA)¢2b2] type: In this
and has no mirror [Link] through the metal or
complex AA represents a bidentate ligand in which two A
centre of inversion. Being unsymmetrical this isomer is
atoms are donor atoms, cz and b are monodentate ligands.
optically active.
Octahedral complexes of [M(AA)cz2b2] type exist in three
geometrical isomers. (ii) Two trams-isomers. In one frcr7es-isomer two NH3
ligands are frcz#s to each other and two Br° ligands
(i) One cis-isomer: In this isomer the two cz groups are cis
are cz.s to each other (See Fig. 7.16). In the other /ro#s-
to each other. Similarly, the two a groups are also cz.I
isomer two NH3 1igands are cz.a to each other and two
to each other. This isomer is unsymmetrical and has no
Br°ligandsaref7-¢73stoeachother(SeeFig.7.16).Both
mirror plane passing through the metal (M) or centre of
these isomers have mirror plane passing through the
inversion. Being unsymmetrical, this isomer is optically
metal, en and NH3, NH3rer°, Br° and hence these give
active.
only super-imposable mirror image. Both these isomers
(ii) Two trams-isomers: In one fra#s-isomer the two c7 are symmetrical and are, therefore, optically active, i.e.,
groups are frcz77s to each other and the two b groups archiral.
are cz.f to each other. In the other /7itz#s-isomer the. two

'''_`i`1u_-
7.36 . Inorganic Chemistry

NH3

Two /ra#s-isomer

fig. 7.16 tis-and trans-isomers of [Co3+(en) (NH2)2Br2]© ion

11. Octahedral complexes of [M(AB)3] type: Here (AB) (ii) The isomer which rotates the plane of polarized light
representsanunsymmetricalbidentateligandinwhichAand towards left (i.e., in anti-clockwise direction) is called
8 are two different coordinating (donor) atoms. Octahedral levorotatory or /-form, /-form is also represented by
complexes of this type exist in c!.s- and frcz72s-isomers. As putting (-) sign before its riame or formula, (+), dextro,
anexample,thecz.s-and/r¢#f-isomersof[Cr3+(gly)3]have and (-), levo, refer to the sign of rotation of the optical
been shown in Fig. 7.17. Each of these foms is optically isomer at the sodium D line wavelength. The d- and
active and hence each has a pair of optical isomers. In cz.a- /-foms have the following characteristics:
isomers two N-atoms and two O-atoms of two gly ions are (a) Since d-and /-forms are capable of rotating the plane
placed at cid-positions while in /7icz#s-isomer these atoms of polarized light, these are said to be optically active
are occupying /r¢73s-Positions. forms or optical isomers and this phenomenon is
called optical activity or optical isomerism. These
ON two forms have exactly identical physical and
chemical properties, although they differ in their
action on polarized light.
(b) d-and /-forms are mirror images to each other just
as left hand is the mirror image of the right hand.
gly0 g'yN Thus d-and /-forms can be superimposed on each
cz.a-isomer /r¢#s-isomer other and hence d-and /-foms are also called mirror-
image isomers. These optical isomers are also called
Fig. 7.17 cis-and trams-isomers of [Cr2+(gly)3]
optical antipodes or enantiomoxphs (Latin; enantio
Since both the forms (i.e., cz.s-and trcz72f-foms) are optically = opposite; morphs = forms) or enantiomers. From
active, each of these forms had c7-and /-forms (optical this description it follows that optical isomerism
isomers). can also be called mirror-image isomerism or
enantiomorphism or enantiomerism.
[Link] Optical (or d*/ or Mirror-Image) I§omerism
(iii)The isomer which is not capable of rotating the plane
Before discussing the optical isomerism shown by various type
of polarized light is called optically inactive. Such an
of complexes we will define some important terms related to this
isomeriscalledmeso,recemic,f7/-or(±)[Link]
isomerism.
substance is composed of 50% c7-and 50% /-form. The
1. Optical activity and optically active complexes: When
solution of a racemic (d/ mixture) fomi in a solvent
the solutions of certain complex compounds are placed in
which contains equinolecular amounts ofd- and /-forms
the path of a plane-polarized light (the waves of the plane-
is symmetrical and hence optically inactive, because the
polarized light vibrate only in one direction; vibrations in rotation (of the plane of polarized light) produced
other directions are cut ofD, they rotate its plane through a
one isomer, cJ-isomer, is balanced or compensated
certain angle which may be either to the left or to the right.
equal but opposite rotation produced by the other (i.e.,
Thispropertyofacomplexofrotatingtheplaneofpolarized
/-isomer). Optical inactivity produced in d/-mixture said
light is called its optical activity and the complex possessing
to be due to external compensation.
this property is said to be optically active.
3. Condition for a molecule to show optical isomerism: A
2. Different forms of optically active complexes: Optically
molecule in which the grouping of the atoms is asymmetric
active complexes are said to exist in the following forms:
is ca,lied a:I+ asymmetric or dissymmetric molecule. ALn
(i) The isomer which rotates the plane of polarized light asymmetric molecule has the following features:
towards right (i.e., in clockwise direction) is said to be
(i) An asymmetric molecule never has a plane of symmetry
dextrorotatory or d-form, d-form is also represented by
(also called mirror-image plane) which is defined as an
placing (+) sign before its name or formula. inaginary plane dividing the molecule in such a way that

ir'`r+{bl,±}flj -+i, `T i{;#ll;il;i\jjJ:` T

 Coordination compounds 7.37

the part of it on one side of the plane is the mirror image Mirror plane

of that on the other side of the plane. The molecules

possessing such a plane of symmetry are always inactive
while those having no plane of symmetry are optically
active and hence show optical isomerism.
(ii) An asymmetric' molecule cannot be superimposed on
its mirror image. `J,,
Thus the most necessary and sufficient condition for a molecule \H4C6,O °\c6H4/C
to show optical isomerism (i.e., to exist in d-and /-forms) is that
the molecule should be asymmetric, (i.e., it should have no plane dextro fom Ievo form
(Object) (Mirror-image)
of symmetry) and should be not be superimposable on its minor
image. Fig. 7.19 Mirror-image isomers of tetrahedral bis (salicylaldehydato)
boron (Ill) ion, [83+([Link])2]+
[Link] Optical lsomerism in Tetrahedfal Complex
Mirror plane
(C.N. = 4)
Here we shall discuss optical isomerism in the following of
cH3)c /CH3
tetrahedral complexes. °\2+/O_c{CH3 0\2+/0 c\\
1. Tetrahedral complexes of [Ma4], [Ma2b2] and [Ma3b] C\ /8\ /C-H HC-H::c
type: Tetrahedral complexes of [Ma4] , [Ma2b2] and [Ma3b] /8\ /C-H
type are not able to show optical isomerism because all the
c6H5/C±C °±C\c6H6 c6H5/C±° °±C\c6H6
possible arrangements of the ligands round the central metal dextro form levo fom
ion, M, are exactly equivalent. (Object) (Mirror-image)
2. Tetrahedral complexes of [Mabcd] type: Since the central
fig. 7.20 Mirrorimage isomers of [Link] bis (benzoylacetonato)
atom (M) in tetrahedral complexes of [Mabcd] type is
beryllium (11) ion, [Be2+(C6H5CO.CHCH3CO)2]°
suroundedbyfourdifferentligands,thetetrahedralcomplex
of this type is expected to produce a pair of enantiomorphs.
[Link] Optical lsomerism in Square Planar Complexes
For example, [As3+(CH3)(C2H6)(S)(C6H4C00)]2 ion
(C.N. = 4)
(tetrahedral) exists in two optical isomers as shown in
Fig. 7.18.
Optical isomerism rarely occurs in square planar complexes, since
Mirror plane they have all the four ligands and the central metal ion in the same
plane and hence contain a plane or axis of symmetry. Thus these
complexes are optically inactive, i.e., they cannot show optical
isomerism even if all the four ligands are different.

[Link] Optical lsomerism in Six-Coordinated Complexes

Octahedral complexes: Here we shall discuss the optical in
octahedral complexes of the following type:
C6H4COO 1. Octahedral complexes of [Ma6] and [Ma5P] type:
Complexes of this type do not show optical isomerism.
Fig. 7.18 Optical isomers of tetrahedral complex ion, [AS(CH3) (C2H5) (S)
2. OctahedraL complexes of [Ma4b2] and [ivla3b3] type: (a)
(C6H4COO)]2
Wehavealreadyseenthatoctahedralcomplexesof[Ma4b2]
Here it may be noted that 4 different groups the central type exist in cz.s- and frcz;€s'-isomers. Both these isomers
metal ion are not the only requirement to make the complex are optically inactive due to the presence of symmetry and
to show mirror-image isomerism. All that is required is that hence do not show optical isomerism, (b) We have already
the molecule should be asymmetric (i.e., unsymmetrical), mentioned that octahedral complexes of [Ma3b3] type exist
i.e., it should have no plane of symmetry so that it can exist in cis (or facial) and trams (or meridional) isomers. Both
in two mirror-image foms. these isomers are optically inactive and hence do not show
3. Tetrahedral complexes of Be (11), 8 '(Ill) and Zn (11) optical isomerism.
with symmetrical bi-dentate ligands have been made and 3. Octahedral complexes of [Ma2b2c3] type: Complexes of
resolved into optical isomers. Some examples of tetrahedral this type do not show optical isomerism.
complexes of this type are bz.a (salicylaldehydato) boron
4.'Octahedral complexes of [Ma2b2C2] type:
[Pt4+(NH3)2®y)2Br2]2+ ion is an important example of
;I::)yf|:[pji83(:i;,6TB.e02|?g60±:]c+oT€fi':c@He3¥3y)[2a]Coet::aot::
mirror-image isomer are given in Fig. 7.19 and 7.20
::tt:tetgaat][ft°4¥#X3):£#r:i2Cf!o#=e¥:sthti::I::::|iy
respectively.
in five geometrical isomers, but only three have been
7.38 Inorganic chemistry

isolated. In cz.a-isomer two identical 1igands occupy the or centre of symmetry, the octahedral complexes of this
adjacent positions of the octahedron. This cz.s-isomer exists type are resolvable into dextro and levo forms. For example,
in two optical (mirror-image) isomers which are mirror- d-and /-forms of [Co3+(e#)3]3+ ion are shown in Fig. 7.23.
[Link]#s-fomofthis
complex ion is symmetrical and hence is optically inactive :#:i:::sTiLedsffd°/Cftoa::raarLe::cmfp+::;)S3]°3£,[%(o4:j3„])#+:
form. Thus it is /r¢#s-J7¢eLso form. [Pt4+(e#)3]4+,[Fe2+(diph)3]2+[Link]
of [M(AA)3] type can be resolved into optical isomers
Mirror plane
Py confirms that these complexes have octahedral shape.
Neither hexagonal nor trigonal prismatic geometry of
6-coordinated complex can give rise to activity.
7.:¥o(34(?:;2ad:2]t+y?oen.C#h]aevxee:ireHa:;es%teedc:#atc:hnL:i:oe:

shows geometrical isomerism and hence exists as cz.s- and

trams-isomers. The cis-isomer does not have any plane or
NH3 NH3 centre of symmetry and hence is optically active, i.e., cz.s-
cis-d-isomer cis-I-isomer isomer can be resolved into two optically active isomers
(Object) (Minor-image) (d- and /-isomers). On the other hand, the fr¢#s-isomer has
Fig. 7.21 Mirror-image isomers of [Pt4+(NH3)2(py)2Br2]2+ ion
a plane of symmetry and hence is optically inactive, i.e., it
cannot be resolved into optically active isomers.
5. [Mabcdefl type complexes: [Pt4+@y)OVH3)Oro2)CIBr2]° Mirror plane
is the only example of octahedral complex of this type. We
have already stated that, theoretically, this complex can exist
in 15 geometrical isomers. Each of these 15 geometrical
isomers exists in optically active d-and /-forms, giving a
total of 30 optically active isomers, d-and /-isomers for one
of the 15 geometrical isomers are given in Fig. 7.22.
Mirror plane
Br Br N
cJ-fomi i.-fomi

[Link]:SuOp::.r:p::s[ecdo:+n(ee:)ca]2o-ti::.Thesecannotbe

Thus fra!#s-isomer is optically inactive (meso-form).

Consequently [Co(e#)2Br2]+ ion has three optical isomer.s
F F viz. (a) Two optically active isomers corresponding to
d-isomer /-isomer cz.s-configuration (i.e., cJ-and /-forms). One form is the
Fig. 7.22 Optical (d-and I-) forms of [Pt4+(py)(NH3)(N02)(CL)(Br)(I)]°
mirror image of the other. (b) One optically inactive form
corresponding to frczJ7s-form (meso-form). All the three
6. [M(AA)3] type complexes: Due to the absence of a plane forms have been shown in Fig. 7.24.

Mirror plane

Br
c„N N
cis-d-isome[ c`z's-/-isomer trams-in eso isome\
(Symmetrical and hence
optically inactive form)

Fig. 7.24 Optical isomers of [Co(en)2Br2]® ion

 Coordination compounds 7.39

Other examples of [M(AA)2a2] type octahedral complexes exists in cz.s-and fr¢#s-isomers (geometrical isomers). Due
whose cz.s-isomers exist in dextro (d) and levo (D forms are: to the absence of plane or centre of symmetry in cz.S-isomer,
this isomer is optically active and hence can be resolved
:::33:((€#2?fi}2d+)'2:Fi:+[(I:Z+?a):8:}]22:']#+t(c:2°4)2CL2]2-> into d- and /-forms. On the other hand, the f7~cz#s-isomer
8.:Fo(34(?i;2a#t3}E:]2C+°L:nT#:ehsa:veHaeL::ayyes::::iact°t:£SsL:oe: has a plane of symmetry and hence is optically inactive,
i.e., frcz#s-isomer is 7"eso-f7'a#s isomer (See Fig. 7.25).

Mirror plane

e„N
Br

N
cz.a-/-isomer trans-meso-\somer
(Syrmetrical)
(Unsymmetrical)

fig. 7.25 Optical isomers'of [Co2+(en)2(NHS)Br]2+ ion

Anotherexampleof[M(AA)2ab]typeoctahedralcomplexeswhosecz.s-isomerexistsincJ-and/-formsis[Rh3+(C204)2Gy)OV02)]2-.
9. [M(AA)a2b2] type complexes: Here we shall consider [Co3+(en)(NI13)2Br2]© ion. We have seen that this ion exists in cz.s- and
/rcz#s-isomers (geometrical isomers). a.a-isomer is optically active and hence gives optically active c7- and /-forms. On the other
hand frcz72s-isomer is optically inactive and hence does not give any optical active isomer, (See Fig. 7.26).
Mirror plane

NH3
N

BrIN

Br Br NH3
cz.s-d-isomer cJ.s-/-isomer /ro7Is-meso-isomer
(Symmetrical)
(Unsymmetrical)

Fig. 7.26 Optical isomers of [Co3+(en)(NH3)2Br2)® ion

[Co3+(C204)OVH3)20V02)2]-ionisanotherimportantexampleof[M(AA)a2b2]typeoctahedralcomplexeswhosecz.s-isomergives
d- and /-isomers.
10. [M(AB)3] type complexes: We have seen that an octahedral complex of this type exists in cz.g-and fra!#s-isomers (geometrical
isomers). Each of these foms is optically active and hence each gives a pair of optical isomers (cJ- and /-forms) as shown in
Fig. 7.27 for [Cr3+(gly)3] complex compound.
Mirror plane Mirror plane

N
trans-d-isomer trans-l-isomer

fig. 7.27 Each of tis-and trans-isomers of [Cr3+(gly)3]° has d and I [Link] isomers
7.40 Inorganic chemistry

Table 7.14 Summary of Geometrical and optical isomerism shown by octahedral complexes (C.N. = 6)
" J fril!ias
Types Of octahedralcamp,ex Geometrical is®merism fy^,

- ae
111111111_

I.
2.
pra6]
[Ma5b] - X

X
X

3. [Ma4b2] [Cr3+quH3)C12]+.[c03+qu3)4cl2]+eta. cz.s- and fr¢7!s'-isomers X

4. [Ma3b3] [c03+on3)3cl3]o2 cz.a-(or fac) and giv¢us-(or X

[Rh3+@y)3C13]° etc.
mer) isomers
5. [Ma4bc] [C03+qu3)2qu20)(C1)]2+ cz.s- and giva7?s-isomers X

6. [Ma2b2C2] [Pt4+qu3)2¢y)2C12]2+ Five geometrical foms. Only cis-d-isomer, cz.s-/-isomer (optical forms), f7i¢#s-
three have been isolated meso form
7. [Mabcedef] 15 different geometrical Each geometrical isomer has d- and J-isomers.
&t;+2#y;]!Cl)(Br)(I) isomers Thus we have 30 optical isomers
8. [M(AA)3] [Co3+(e#)3]3+ etc. X d- and /-isomers
9. [M(AA)2a2] [Co3+(e„)3C12]+ etc. cz.a- and giv&z!s-isomers (cz.s- Being unsymmetrical, cz'£-isomer gives cj'S-d- and
isomers is unsymmetrical) cis-/-isomers (optical isomers)
10. [M(AA)2ab] [Co3+(en)2qul3)(Cl)]2+ cz.s- and givtz7ts-isomers Being unsymmetrical, cl.£-isomer gives cj.s-d and
etc. cz.s-/-isomers (optical isomers)
11. [M(RA)a2b2] [Co3+(e#)qu3)2C12]+etc. cz.s- and Jr¢jfs-isomers c.I.s-isomer exists as cz.s-d-and cis-/-isomer (optical
isomers)
12. [M(AB)3] [cr3+(gly,3]0 cz`s- and Z7i¢#s-isomers qach Each geometrical form is optically active. Hence
fom is optically active) cis-form gives cis-d-and c!.s-/-optical isomers.
Similady giv¢#s-fom gives frczus d- and f7i¢72£-/-
optical isomers.

Table 7.15 Summary of geometrical and optical isomerism shown by tetrahedral and square planar complexes (C.N. = 4)
a 7?z 7£?`;€ r3 s x>g?I;i "3a3r :£ass&? ys:}`6+asi&x:*st*:ise?n8*grr;`$4gex§|: :,. ;``. ^`)s3 :,` y

i Typesofcomplexes
(A) Tetrahedral complexes
I. [Ma4] X X

2. [Ma3b] X X

3. [Mabcd] e.g.[As3+(CH3)(C2H5) (S)(C6H4C00)]2- X Two optical isomer

4.£:a:£[se:.egs.:£3:{:D6fr:£[;r}ce£C..cC£:gin)i,n]8aunnds¥Bng(ec¥fia4]obt-£eon)t,a]t+e X d- and /-isomer

q}) Square planar complexes X Square planar

I. [Ma4] complexes rarely showOpticalisQmerism

2. [Ma3b] X

3. [Mab3] X

4. [Ma,t],I e.g. [Pt2+qu3)2CIO]° c!.s'- and Jr¢zzs-isomers

5. [Mabcd] e.g. [Pt2+owl)¢pr)(Cl)(Br)]° Three isomeric forms
6. [Ma,bc] e.g. Pd2+Cl,Brl]2-, [Pt2+¢ry),(NH3)(Cl)]+ cis- and givtz#s-isomers
7. M(AB), e.g. [Pt2+(gly)2]° (gly-ion is NH,.CH,COO-) c!.a- and frtz#s-isomers

ptically inactive.

ese are asymmetric. (ii) These are optically

d hence is optically active ®pde ally active.

isomer) is symmetrical and hence is optically inactive. Being Optically

meso form«
 Coordination compounds 7.41

11 isomer of Ni(NH3)2C12 does not react with C2042-ion means

that the 2 C1° are present at trans position.

complexes having two different types of unidentate ligands

central metal ion?
- No reaction
;i . 'i . Tetrahedral complexes do not show geometrical isomerism
because the relative positions of the unidentate ligands attached
to the central metal atom are the same with respect to each other.

Hence I is
In the reaction,
[COC12(NI13)4]© + Cl© - [COC13quH3)3] 3, Only one
isomer of the complex product is obtained. Is the initial complex cis-diamminedichloridonickel(II)
cis or traus?

In the original complex, two-C1° ions are present in the

....`.`.:; and 11 is
trams position, so that all four NH3 molecules are equivalent and
replacement of any one of them gives same product.

trams-diamminedichloridonickel(II)

g pair of isomers be

b.I. [Cr(NH3)6] [CrQq02)6] and

11. [Cr(NI13)4(N02)2] [Cr(NHS)

HiHue
a. I can be distinguished from 11 by electrolysis of their aqueous
When[NI(NI.13)d2+istreatedwithconc. a coxpounds solution.
the formula (design
formed). I can be converted into 11 by (I) E± [C00JH3)6]:a+q) + [CroJ°2)6]:a-®
solution of I reacts with oxalic acid to fi [Co(NH3)6]3+ will migrate towards anode and is deposited
11 does not react with oxalic acid. Deduce on anode.
I and 11 and the geometry of Ni(II) complexes.
(||) _ [Cr(NH3)6](3:) + [CO0V02)6]:a-q)
illRE INiorH3)4]2+ + Hci - Niou3)2ci2
Onelectrolysis,[Cr(NH3)6]3+ionwillmovetowardsanode
cone. (I and ll) and is deposited on anode.
I [Link] >11 b. (I) and (11) can be distinguished by conducting measurements
I oxalic acid> NiquH3)2(C2°4) (I) will show conductivity as (3+, 3-) electrolyte whereas
(11) will conduct electricity as (+1, -1) electrolyte.
[[ oxalic acid> No reaction
C2042-ionisactingasabidentateligand,andformschelatering,
since I isomer of Ni(NH3)2C12 form Ni(NH3)2C204 this indicates
that two C1® ions in I are present at cis-position.

H3(NLT}T'
fiiEue The two geometrical isomers (a) and (b) are of the type
H3N
[M(AA)2 b2]"± , so (a) cis-isomer is chiral (optically active).
The two entities are represented as:
7.42 Inorganic chemistry

16. [M(AB)3]"±: AB is unsymmetrical bidentate ligand, e.g.

--=---=-:
[Cr(gly)3]

(a) cz.a-form (a) cz.s-fom

d-I_

Optically active cis- o AL trans-

(Optically active)
Thans-form is optically inactive, due to the presence of plane of
symmetry as shorn: Both forms are optically active.
17.P[:::;:[oe{§°:;P;[Link]n])S2j4S+h°W°Pt]Ca]actlvlty9e8

-p-I:n-e-Zsin-merry

twchc:dads
11. [Ma3b3]n±. e.g. [COC130VH3)3]

c!.a-or facial (fac) frcz#s' or Meridoinal (mer)

OIA (Optically inactive isomers)
12. [Ma2b2C2]"±, e.g. [PtoJH3) (H20)2 Br2]2+

cis-isomer

NH3

[Link](aehdetg]a6,C:eT,Pe[tehxye]Se::ndtfaa]:]£::ttetrxaaadceen:::ec]ig::da:::i;I.;

ion, also shows optical isomerism,

OH2

cj.s'-d-isomer cz`s-/-isomer

Optically active due to non-superimposable mirror image.

13. [Mabcdef]"±: If the central atom is asymmetrically
coordinated, each of its 15 geometrical isomers should be
resolved into optical isomers, e.g.

[ptclBr orH3) o{o2) ®y)I]

Only 3 isomers have been prepared till now, no form has
been resolved.
14. [Mabcd(AA)2]"± type
Note: The total number of N{rLO bond angles in [Cr(edt&)
e.g., [Cr+3Br-[Cl-I (CRT')(H20°)(en°)] complex ion is 8, as shown below.
shows 12 optically active isomers. There are 2N-atom OVL and N2) and 4 [Link] (o3, o4, o5, o6).
15. [Ma2b2(gly)]"± type So total 8 N-Cro bond angle are possible as given below:
e.g., [Cr+3C12~2Br2-2(giy-I )]2- 1. N]-Cr-03 2. N]-Cr-04 3. N]-Cr-05 4. N]-CrL06
shows 4 optically active isomers. 5. N2ir_03 6. N2_Cr_04 7. N2_CrL05 8. N2Cr_06
 Coordination compounds 7.43

Moreover, (N{r-N) bond angle = 1 is the linkage isomer of [Co(SCN)(NH3)5]C12

(O-Cr-O) bond angle = 6. Pentaamminethiocyanato cobalt (Ill) chloride

iii.SinceN02©ionisanambidentateligand,thegivencomplex
ion has two linkage isomers. The structures of these isomers
[Link](C)N02°ion(1igand)islinkedwith
the central Co3+ ion through its N-atom while in its isomer
(C]) it is linked with Co3+ ion through its O-atom.
2+

H3T,`:I:23:?NH3
.`....```.`:..`

(C)=
i. The coordination isomer of (A) is [Cr(en)3] [Co(CN)6].
The stnicture and name of the above two isomers are given
below:

(A) = Tris (ethylenediamine)cobalt(Ill)

hexacyanochromate (Ill) and its. isomer
Tris (ethylenediamine) chromium(Ill) hexacyanocobaltate (Pentammininenitrocobalt (Ill) ion)
(Ill)
NH3
ii. Coordination isomer of(B) is [Cr(NH3)6] [CO(C204)3]. The
structure and name of these isomers are given below:
(8) = Hekamminecobalt(Ill) tris (oxalato)chromate(Ill) (C,) 3 CoJT ,
and its isomer.
[CrovH3)6] [CO(C204)3] is
Hexamminechromium(Ill) tris (oxalato)cobaltate(Ill).
(Pentamminenitritocobalt (Ill) ion)

Draw the structures and write the names

isomers of: The complex ion a substitution
i. (A) [Pt(SCN) (NH3)3] SCN reactionwhenreactedwith(NaN02+Hcl).Anunstablescarlet
ii. (8) [Co(SCN) QVH3)5] C12
red complex A is formed when dilute acid is used and a stable

iii. (c) [cOINH3)5aro2)]2+

yellow complex 8 is formed when concentrated acid is used.
Both A and a are isomeric ions, Give the
Sch. structures Ions un involved
i. (A) has one .linkage isomer A] which is
illERE Since the treatment of (X) (NaN02 + dil. HC1) gives an
unstable red complex, this red complex should be pentaammine
LP]tt(hNpcfs+)£¥::3£::]Nrie:{fo]n)i:£:uNgi°nne(g[::;:e:i:::lag:: nitritocooalt (Ill)ion, [Co3+QVH3)5 (ONO)]2+.
N-atom. Thus the structures and names of these linkage Similarly, the ion obtained by treating [Co3+(NH3)5 Cl]2+ (X)
isomers can be written as given below: ionwith(NaN02+[Link])shouldbepentaamminenitrocobalt
H3N+:;:r3
i[i[u)sL°£'=[::::gr#:)T(:*];;i2+and
(A)=
a = [Co3+ OVH3)5 qu02)]2+.
Obviously A and 8 linkage isomers and the isomerism involved
is linkage isomerism.
(Triamminethiocyanatoplatinum(II)thiocyanate)

H3Nf`:;:PHS
What type of iso are the following:
(A1) =

\,;
------- N9-c-S':
scNe J}] and [Mn(CO)5
[Cr(CN)6] and [Crfen)3] [Co(CN)6]
15N03] S04 and [CO(NH;)5S04]N03
(Triammineisothiocyanatoplatinum (11) thiocyanate,

[(Pt OVCS) qu3)3] SCN

ii. [CoOVCS)(NH3)5]C12

(Pentaammineisothiocyanato cobalt (Ill) chloride)

7.44 Inorganic chemistry

fiHEhii
I. a. The given complexes are linkage isomers, since these
Draw all possible isomers Qf:
complexes have ambidentate ligand viz. Schp ion.
i. PtquH3)4C12]2+
b. The given complex compounds are coordination isomers,
iii. [Pt{P(C2H5)3} C]2]2
since each of them contains complex cation and complex
anion as shown below and these complex compounds can A - ,,

be obtained by interchanging the ligands present in complex i.PtovH3)4C12]2+ion:Thisionisanoctahedralionof[Ma4b2]

cation and complex anion.
C omp lex Complex Complex #:=s:¥:nccz.:_::::e:g:mce,#|:S:r::nscvz.;Z.::Ss#:ntr:::
compound cation anion in frcz#s-isomer these ions have /r4#s position.
[CO(en)3] [Cr(CN)6] E [Co(en)3]3+ + [Cr(CN)6]3- CI
2+

[Cr(en)3] [Co(CN)6] a [Cr(en)3]3+ + [Co(CN)6]3- H3T,\-I,:+3-7, H3Ti\-p|t4-+-?NH3

c. These are ionisation isomers, since they give different ions
in aqueous solution as shown below:

[cotNH3)5No3]so4 a [coavH3)5N03]2++ s042- H3Nq-`,`Cl H3NJ4-*H3

(I) NH3 Cl
[COO+H3)5S04]N03=[CO0VH3)5S04]©+N03®
[Link]-isomer fr&»s-isomer
(11)

(I) gives S042~ ions and (11) gives N03© ions. Complex
£E.I:t;gh`£yc)h2]:iy[6]:oansdrufir2e.3'H:.a€8°om9P':sxa°nf|#s(y£2e]tr¥a:
cations given by them are also different. Due to the
bidentate ligand. This complex has two geometrical isomers
production of SOS- ions, (I) gives a white precipitate of
viz cz.s and frcz#s.

:h:St?s4t#£83ao:;2n::]ut]°n.°ntheotherhand,(||)gives N

d. These compounds are hydrate isomers, since they contain A-p-,2-+-fi A_--._-A
different number of H20 molecules inside and outside
c oordination sphere.
00
[Cotoy)2(H20)2C12]C1±[CO®y)2(H20)2C12]®+Cl© cz.s-isomer J7i¢r!s'-isomer
Electrolyte (I)
iii. [Pt{P(C2H5)3}C12]2: It is a bridged binuclear planar
[CO®y)2(H20)C13] .H20 a No ionisation complex and exists in three isomeric forms viz cz.a, /rtz#s
Non-electrolyte (11)
andunsymmetrical.
11. a. The given complex compounds are coordination isomers,
since each of them contains complex cation and complex
anion as shown below and these isomers can be obtained (C2H5)3:I)Pt<:)Pt<:([C2H5)3
by interchanging their ligands. cj.s-isomer
a C omp |ex Complex C omplex
(C2H5)::>Pt<>Pt<:;C2H5)3
c ompound cation anion
[CroJH3)6] [Cr(CN)6] a [CrovH3)]3+ + [Cr(CN)6]3-
frc!#s-isomer
[CroJH3)4 (CN)2] [Cr(NH3)2 (CN)4] a
[Cr(NH3)4(CN)2]® + [Cr(N113)2(CN)4]°
b. The given complex compounds are ionisation isomers,
:>pt<>t=:(::::;:
unsymmetrical-isorner
since they give different ions in aqueous solution as shown
below: iv. [CrovH3) (OH)2C13]2-ion: [Ma3b2c]"± [Link] ion has
three geometric isomers.
[Pto{H3)4Br2]C12±[Pto¢H3)4Br4]2++2C|° 2-
CI
(I)
[Pt(NH3)4C12]Br2E[PtovH3)4C12]2++2Br°
oT,\-cl:+-71
(11)

(I) gives C1° ions and (11) gives Br®ions. (I) gives white
[Link],
(11) gives yellow precipitate ofAgBr with AgN03 solution.
i,-\;H
a. Cli:I cz.a, OHroH c!'s b. Clil f#¢#s, OHLOH frczHs
 Coordination compounds 7.45

c. Cl{1 frtzJts, OHcOH cis

I. Neither optical nor geometrical isomers c

[Link] spectroscopy. Why?
•11. Select the pairs of
rical isomers

HHif
I. Since all atoms in each isomers are attached to the sane
other types of atoms, the same fragments are expected when
the molecules are split.
Therefore ultraviolet (UV), nuclear magnetic resonance
(NMR) and X-ray diffraction, conductance method,
electrolysis method, chemical method, dipole magnetic and
• magnetic properties method are used to distinguish isomers.

11. a. Geometrical isomers are 1 and 3,

4 with 6 and 8
7 with 6 and 8
5 with 6 and 8.
b. Optical isomers are 6 and 8.
c. Identical structures are 1 and 2,
4, 5 and 7.
Ill. A. Geometrical isomers
8. None
C. None
D. None
E. Optical active isomers
7.46 Inorganic chemistry
`f'- iS.
Ill. [Zn CI Br (CN)OrH)3]y rv. [Cr(Brcl)(H20)4] [Ag(CN}2]
I. [Ma5b,"± type: V. [Cr Br2(H2Q)2qu3)2] Ct
Structural isomers = 0
§.` .`i-..`.:

Geometrical isomers = 0
I. It can exhibit linkage and geometrical isomerism.
Optical isomers = 0
11. It can exhibit geometrical isomerism. Does not exhibit
11. [Ma4b2]"± type: structural and optical isomerism.
Structural isomers = 0 Ill. It exhibits optical isomerism
Geometrical isomers = 2 IV. [Cr(Brcl)(H20)4] [Ag(CN)2] and
Optical isomers = 0
[Crcl(CN)(H20)4] [AgBr(CN)] are coordination isomers.
Ill. [M(AA)2b2]"± type: V. It exhibits ionization, geometrical and optical isomerism.
Structural isomers = 0
Note: [Cr Br2 C1 {H20)(N113)2], H20 is not hydrate isomer of
Geometrical isomers = 2 [cis 3 c7 and / trams => meso] the complex rv)
Optical isomers = 3
Total stereoisomers = 3
IV. [Ma2bc]"± types, (square planar)
Structural isomers = 0
Geometrical isomers = 2
Optical isomers = 2
Total stereoisomers = 2
•, " T `!.I

V. [M(AA)2bc]"± type:
I. It does not exhibit geometrical and optical isomerism
Structural isomers = 0 because it contains plane of symmetry.
Geometrical isomers = 2 (cz.s 5 c7 and / Jr¢#s 3 meso)
Optical isomers = 3
Total stereoisomers = 3.
VI. [M(AA)2b2]"± type:
Structural isomers = 0 H2
Geometrical isomers = 2 (cia 3 d and / f7i¢7cF ==> meso) 11. It exhibits optical isomerism.
Optical isomers = 3 Number of stereoisomers = 2
Total stereoisomers = 3. (acac)© i Acetyl acetonato ion
VII. [M(AA)3]"± type: oeo
Structural isomers = 0 Ill

Geometrical isomers = 0
(CH3-C±CH-C-CH3)
Optical isomers = 0 H3C
\;c-c\
eo
H3C\ \
HC
\c :3,¥::-€j'=:3H3
-+,,
CH3 eo>czCH
•.s#.;.`.?...
H3C
I. No. of stereoisomers = 3, cis = 1, trans = 2.
(OR)
11. No. of stereoisomers = 3, All geometrical isomers.
Ill. No. of stereoisomers = 2, Both are in d and / fomis
IV. No. of stereoisomers = 0.
 Coordination compounds 7.47

Ill. It exhibits optical isomerism.

Number of Stereoisomers-2 ii.[€3r(o-X)(eon)2][+[€3(O-£)2(eon)]'-

H2e eH2
H2c-N\za/cN CN\z£/N-CH2 iii.[€3O(O-x)(eon)2]l+[a3r(o-£)2(en)]]-

iv.[53o(eon)3]3+[63r(o-X)3]3-
o±c-oe/ \NH3 H3N' \8-Lo
i

11. Total coordination isomers = 4

d-fom '-form
i.[*3£(eon)3]3+[63O(c-fr)6]3-
IV. Hybridisation of Pd2+ is cJsp2. Complex has plane of
symmetry hence does not exhibit optical isomerism. But it ii.[iv3i(c-i)2(eon)2]1+[€3O(c-fr)4(eon)]]-
exhibits geometrical [Link] number of geometrical
isomers = 3. £;i.[€3O(c-i)2(eon)2]1+[*3i(c-fr)4(eon)]]-

iv.[63O(eon)3]3+[iv3i(c-fr)6]3-

111. Total coordination isomers = 2

i. [!:(H:o)4]2, [5i #-
[Ptc12(H20)2]
ii.[€:i[(H:O)3]1+[5:i33(H:o)]]-
III.[!i(eon)3]3+
V. [M(en)2]
VII. [M(Sly) quH3)2]

I. 3 2 stereoisomers (dy2)
11. 3 3 stereoisomers (d2sp3)
Ill. 5 2 stereoisomers (d2sp3)
IV. 3 2 stereoisomers (sp3)
V., VI. and VII. does not show stereoisomerism. When fifiEHus (2) For [Ma2bcde]"± type:
symmetrical bi-dentate ligand present in coordination I = No. of cis isomers = 6
number of 4, it does not show stereoisomerism. y = No. of trans isomers = 3

i = £=2
J,3
How many geometrical and stereoisomers are ssible for
I. [Mabcd]rfe and
||. [Mabcdeflrfe type compounds respecti
J=

I. [Mabcd]"± type i 3 geometrical isomers no optical isomers.

11. [Mabcdefr type i 15 geometrical isomers and each isomer
is optically active.
Total number of stereoisomers for 11. = 15 + 15 = 30

Sol,
I. Total coordination isomers = 4.

i.[a3r(eon)3]3+[6;(O-&)3]3-
 7.48 Inorganic chemistry

ue (6) For [Mab (AB)2]"± type

(where AB is unsymmetrical bi-dentate ligand e.g. ; glycinato:)

No. of geometrical isomers = 6 (2 cis + 4 trams).

\.````i.`-`.`

I. No of stereoisomers = 4 (cis and trams & both optically

active)
Trans isomers :

>i5 (:=13: (:=8:

T±
cj.s-form fra#s-form
(d 8L D (d & r)
optically active optic ally active

11. No. of stereoisomers = 6 (1 cis 3 optically active 4 trans 5 all optically inactive)

bbbb

1 :=i=:1l :=[=: ,11 :=\=:lv :=\=: V :=\=:

C bc bc
cia-form
(d 8L D All trans-fom
optically active All optically in active

Ill. No. of stereoisomers = 3 (All optically inactive).

a
I H=C;`f_E|+2,8-c=o
•1 :>¥<: 11, :>¥<: o-c-8-Pt`N-t=---H
:=\=: (traus)
ri2 _`CH3
C a.
cis-form '&„s-fom
H

I,, H3;+±`:=§>i2<§=±oCH3
(cis)

H2 e
£V. -O-C-O
H3c~`f-N-` +2
o-c-8,Pt
(trans)
THTd<.:H3
HEfiB (1.33) )/ = No. of stereoisomers in 11 = 3 [1 cis = optically active,
I = No. of Geometrical isomers in (I) = 4 (2 cis + 2 trams) 1 trams = optically inactive]
H3C. .H

H;`rE2`+2 ,#2i<cH3 acac° = acetylacetonato ion ECH-S=cH3)

CH3-C=CH-C-CH3
o=c-o'Pt`o-c=o
(cis)

ffiEEJ'tELid ' L ,I „' I I' _ I : I I `"+ Li+S>.:i::¥!L;'[i.J'T\t':LL§

 Coordination compounds 7.49

Br of the electron around the nucleus in orbitals and hence magnetic

H3C\
moment due to orbital motion of the elctron is quenched tr, = 0)
;C=°\tE3<)o±C-CH3 and hence vi{;iiJ = 0. Thus magnetic moment of an unpaired
HC>c_eo,Lc±cH
electron residing in 3d-orbital of ions of 3d-series is

H3C u = 2JiGTTT)BM

s = i(forone electron)
CH3
cis-tom (d & D
optically active u=2
•Br
H3C\ For # unpaired electrons, #eff is given as
C-O\ -C\/CH3
HC
[i3<: -c\cH3
\,c-eo,
/ CH
„eff = 2

/` Since#effisonlyduetothespinmotionof#unpairedelectrons
CH3
it is also called spin only magnetic moment and is represented
trams-form as „s.
optically inactive
ueff = us= Jfro) BM
• i = ±=1.33 The above equation shows that value of #eff depends only on
J,3 the number of unpaired electrons present in the species.
Greater is the number of unpaired electrons present in orbitals
7.9 MAGNETIC PROPERTIES 01= of central metal atom/ion, greater is the value of #eff as Shown
below:
COORDINATION COMPOUNDS Number of unpaired Magnetic moment trs) in Bohr
The transition metal complexes whose central atom/ion contains electrons magnetons
oneormoreunpairedelectronsareparamagneticwhilethosecentral 0 0
atom/ion which have no unpaired electrons (i.e., all electrons are •!FI- - \.T3`
1
paired) behave as diamagnetic substances. Paramagnetic character
increases with increase in number of unpaired electrons. The 2 JT--z.83
paramagnetism of a complex is expressed in terms of magnetic 3 jTE5-3.$3
moment tr). Greater is the number of unpaired elections in the 4 Jri4-4.90
central atom/ion of given compound, greater is its paramagnetic
5 Jis5-5.92
character and hence larger is the value of magnetic moment of
the complex. The magnetic moment is expressed in terns of Bohr
Magnetons (BM). Paramagnetic substances have some value of
magnetic moment whereas diamagnetic substances have zero
magnetic moment. Terminology
For transition metal complexes, I. Write the formula of the following compounds according
ft,--H1+us to the IUPAC rule.
where#, = orbital magnetic moment, i.e. magnetic a. Potassium tetraxoferrate(IV)
moment due to orbital niotion of electron. b. Potassium tetrazidocobalt(II)
c. Dichloridobis (triphenylphosphine) nickel(II)
4s = Spin magnetic moment, i.e. magnetic moment
due to spin motion of electron. d. Chloridocarbonylbis (triphenyl phosphine) iridium(I)
efe e. Hexammine cobalt(Ill) pentachloridocuperate(II)
„ = [viin + 2rfu] 47tm f. Tetrammine-# -dihydroxobis (ethylenediamine)
= [vifro + 2jdr] B.M. dicobalt(Ill) chloride.
9. Dibromidotetra ammine cobalt (Ill)
BM is Bohr Magneton. tetrachloridozincate(II)
cfe
1BM- h. Hexammine nickel(II) hexanitrocobaltate(Ill)
47tm
i. Hexammine cobalt(Ill) tetrachloridodiammine
where e = charge on electron chromate(Ill).
A = Plank's constant 2. Name the following compounds:
" = mass of electron a. [Fec12qu20)4]© b. [Cr(en)2C12] CI
In case of transition metal ious of 3d-series, the crystal fields C. [Pt(Py)4] [Ptc14] d. [CO(en)2(CN)2]C103
(i.e.,theligandssuroundingthemetalions)restrictthemovement
7.50 Inorganic chemistry

e. csTeF5 f. [coorH3)5co3]2 [cucl4]

(b) Which of the following is an oxidizing agent and
9. NaMn(CO)5 reducing agent.
(I) Fe(CO)9 (II) Mn(CO)6
][(en)2C°fo:>co(en)2]3h+°VH4)2TIC16 (Ill) Mn(CO)5 (IV) Mn2(CO) I o
Conductance in Coordination Compounds
11. Arrange the following in order of increasing conductivi
i. [Cr(acac)3] k. gNi(ding)2]
in solution.
I. Snc14 (Et2NH)2
a. PtquH3)6C14 b. Cr(N113)6C13
3. Give the characteristic coordination number of each of
the following central metal ions: c. coorH3)4ci3 d. K2ptci6
a. Cu(I) b. Cu(II) [Link](NI13)3qu02)3
c. Co(Ill) d. Al(III) In aqueous solution, one of these conducts electricity whil
e. Zn(II) f. Fe(II) the other does not. Deduce their probable structures.
8. Fe(III) h. A8(I) Isomerism in Coordiation Compounds
4. Indicate the oxidation state of the central metal ion in 13. How will you distinguish between the following pairs o
each of tne following complex.
isomers [CrorH3)3(No2)3] and [Cr(N113)6] [Cravo2)6].
a. [CuquH3)4]2+ b. [Cu(Br4)]2- 14. How many geometrical isomers are possible for the comple
c. [Cu.(CN)2]e d. [cravH3)4co3]© ion [crorH3)(oH)2cl3]2-.

e. [ptcl4]2- 15. The Complex M(C204)C120VH3)2 forms two types of ioni

f. [coquH3)2quo2)4]e
coloured crystals viz., red (A) and blue (8). Both A an
8. Fe(CO)5 h. [Znc14]2- a reacts with 1 mole of AgN03 to give 1/2. mole of a r
i. [Fe(en)3]2+ precipitate. Further i mole of A reacts slowly with 1 mol
5. Calculate the freezing point of the solution containing of Ag2C204 to form 2 moles of a white precipitate but
24.8 g solute per kg water for each of the following does not react with Ag2C204. From the above data. Find
solutes; Kf = 1.86 QC/in a. the coordination number of M
a. [coon3)3oro2)3] b. the hybrid orbitals of M and
b. [cO(N113)4oro2)2] [cO(NH3)2oro2)4] c. stereochemistry of red and blue forms
c. [coquH3)5oro2)] [co(NITS)2(No2)4]2 [Link](en)2¢`ro2)2Clhasbeenpreparedinthes
isomeric forms A, 8 and C. A does not react with AgNO
[Mw of (a) 248 g a) 496 g (c) 744 g]
or (en) and is optically inactive. 8 reacts with AgN03 bu
Effective Atomic Number (EAN) not with (en) and is optically inactive. C is optically activ
6. Calculate FAN in andreactswithbothAgN03and(en).Identifyeachofthes
a. [Cr(CN)6]3- b. [Pdc14]2- isomeric forms and draw their structures.
C. [PtovH3)4]2+ d. [Cu(CN)4]3- 17. A solution containing 1 g of the complex
7. Calculate "BAN" of metal atoms in the following: [Cr(H20)5Cl]C12.H20 Was Pas;ed through a catio
a. Fe(CO)5 b. C02(CO)8 exchanger. The acid liberated was made up to 1 litre
c. Fequo)2(CO)3 d. Fe(C5H5)2 Calculate the strength of acid solution. (Aw of Cr = 52 an
Mw of complex = 266.5 g mol-I)
8. Predict the value ofx in each of the following carbonyls:
18. A solution containing 2.675 g of CoC13.6NH3 was passe
a. Co2(CO)I b. HX cr(CO)5
through a cation exchanger. The solution obtained gav
c. Hx Co(CO)4 d. Mo(CO)I
[Link]
g. („ ::3o,TE;efi:||Coo#i::#w[iFci(,: =|:5Ti'Afflth-enc:T|5u): the fomula of the complex.

of expression "x + y + z" is (Mw of CoC13.6NH3 = 267.5)

@) If complex [Mn (CO)I (t|y - C5H5)] follows EAN

rule, then value of expression "x + y" is
(c) Calculate the BAN of central metal atom/ion in the
7.10 B0NDING IN COORD[NATloN
fol lowing species/camp ound. COMPOUNDS: VALENCE BOND
(I) [CoBrl(Trien)]® (II) INi(din8)2]
THEORY (YB_I,
(Ill) [Cr (e#)3]3+ (IV) [Ca (EDTA)]2-
[Link]
on INi (co)4] rvl) [Fe (cN)6]4- involved in this theory are as follows:
10. (a) BAN of co (CO)4 is 35 and hence is less stable. How
a. Orbital hybridisation: The model utilises the hybridisation
it ,attains stability.
of s, p and c7 valence orbitals of central metal atoms or
 Coordination compounds 7.51

ions (in which electron pairs donated by the ligands are yy:^ , Aftbmi€
nra a",;art:.^`oa: i: A
',:z :o{,`:r,\r\ ^ rty rifts
accommodated) to account for observed structures and
magnetic properties.
21 Sc 3dt 4s2
b. Bonding between ]igand and the metal atom or ion: From Ti 3d2 4J2
22
the valence point of view, formation of complex involves
reaction between Lewis bases (1igands) and Lewis acids 23 V 3,1`` +```-

(metal atom/ion) with the formation of coordinate covalent 24 Cr 3d5 4S`

(or dative) bonds between them. 25 Mn 3d5 4$2

c. Relation between the observed magnetic behaviour and 26 Fe 3d6 4$2
the bond type: That is, the geometry of coordination entity 27 Co 3d7 4$2
can be predicted of its magnetic behaviour is known.
28 Ni 3d8 ds2

29 Cu 3dlo dsl
7.10.1 ASSUMPTIONS OF VBT
30 Zn 3Jlo ds2
i. The ligands have at least one a-orbital containing a lone
pair of electrons. ii. For coordination number 4, the hybridisations possible
ii. Metal-ligand bond (L+M) arises by the donation of pairs are sp3 and c7sp2, having tetrahedral and square planar
of electrons by ligands to the empty hybridised orbitials of geometries respectively, while for coordination number
central metal atom or ion. It is basically overlap of atomic 6, the hybridisations possible are c72sp3 and sp3# having
orbital of both the entities. octahedral geometry in both the cases.
iii. In order to accommodate these electrons, the metal ion must iii. There are two types of ligands namely strong field and weak
possess same number of vacant orbitals of equal energy. field. A strong field ligand is capable of forcing the electrons
These orbitals of metal atom (s,p or cD undergo hybridisation of the metal atom/ion to pair up (if required). A weak field
to give a set of hybrid orbitals of equal energy and with ligand is incapable of making the electrons of the metal
definite directional properties. These vacant hybrid orbitals
atom/ion to pair up.
now overlap with the ligands to form strong coordinate
iv. Some ligands have been arranged below from the weakest
bonds.
to the strongest. This'arrangement is called spectro chemical
iv. The non-bonding electrons of the metal occupy the inner
series as shown below:
orbitals. They are grouped in accordance with Hund's
rule. However, under the influence of some strong ligands, |©<Br°<S2-<SCN©<C1©<F©<N03°<8H<urea<EtoH
there may be some rearrangement of inner electrons in the Weak field ligand
atomic orbitals (against Hund's rule). During rearrangement
<C2042-(OX)<02-<H20<NCS°<EDTA<NH3
generally pairing takes place and consequently some
orbitals are vacated and made available for hybridisation. Border line field ligands

v. (For octahedral complexes only) The c7-orbitals involved in

thehybridisationmaybeeither(#-1)d-orbitalsor#c7-orbital =¥hHe3:¥*:i;8=e¢h#e:e€;armine(en)<dipyndyi(d]py)
(# refers to the outermost principle shell of the central metal Strong field ligands
atom). The complexes fomed in two ways are referred to
as inner orbital complex (or entity) or outer orbital complex
(entity). On the basis of spin they are also referred as low
spin and high spin complexes respectively.
vi. If a complex contain unpaired electrons, it is paramagnetic
in nature, whereas if it does not contain unpaired electrons
it is diamagnetic in nature.
vii. Square planar, tetrahedral and octahedral complexes
are formed as a result of c7sp2, sp3 and c}2sp3 (or xp3d2)
hybridisation.

7.10.2 TYPE OF GEOMETRY (STRUCTURES)

OF COMPLEX ENTITIES

In predicting the geometry of complexes, the following points

are helpful:
i. Electronic configuration of first transition series:
7.52 Inorganic chemistry

Table 7.16 Some important types of hybridisation and

Ni2+ in INi(CN)4]2-
their geometry
c7sp2 hybridisation (4
coordi- Types of Geometry+ ^Examples^`
nationnumber h¥bridisation ^ ndth5 --complex
:'y[Link]ncp#S;:::)ated
2 sp (4S, ftyx) Linear K[Ag(CN)2]',Agqu3,2]®[cucl2]©'[CuOu3)2]®
Since the complex is diamagnetic, the two unpaired electrous
in 3cJ, gets paired up making available one vacant 3d orbital.
One 3d, one 4s and two 4p orbitals hybridise to give four
dsp2 hybrid orbitals and these orbitals now participate in
3 Sp2(4S,4p„4py, Trigonalplanar K[H813]
sigma bond formation with the ligands. Thus [[Ni(CN)4]2-
ion has square planar geometry and such no unpaired
electron is there, it is diamagnetic.

4 dfp2 Square i. CN° being a strong ligand forces pairing ofelectron to

2-half filled 3d orbitals
(3Jx2_}2, 4s, 4p„ 4py) planar Ft£&N3)f4]]22-+
ii. Hybridisation: c7sp2
4 sp2d Square [CuOu3)4]2+ iii. Geometry: square planar
(4S, 4Pr, 4Py, 4d*2_y2) planar iv. Number of unpaired electrons = 0
v. Diamagnetic
4 sp3 Tetralie-
(4S, 4Pr, 4Py9 4Pz dial ¥£:4i2,-;]3-,INi(CO)4] Vi. #s=zeroBM
2.[Nic14]2-ion:ThiscomplexionhasNi2+ionwhosevalence
5. dsp3 Trigonal shell configuration is 3d8 4s°. Magnetic measurements
bipyraml-dal
(3dz2, 4S, 4Px, 4Py, 4Pz) [Ei(gl?]T£], reveal that the given ion is paramagnetic. This is possible
only when this ion is fomed by sp3 hybridisation and has
5. sp3d Squarepyranidal [sb F5]2- tetrahedral geometry.
ds4p
3d
mm
lm
Ni atom (3d8 4s2)

6. d2sp3 Octahe- Ni2+ ion (3d8)

(3d „2_),2, 3dz2, 4S, 4P#, deal
4py, 4pz) (lamer-orbitalcomplex) Ni2+ in INic14]2- ion
tH REt
iii(&i:;i6:i;+:, xp3 dybridisation
6. sp3d Octche- (4 electron pairs
donated by four
4s, 4Px, 4Py, 4Pz9 dial(Outer-orbitalcomplex)
cl© ious)
4d x2._if e, 4dz2 :::,::!2:;,66]]22++,
i. Cl© is a weak ligand, so no pairing ofelectrons occurs.
ii. Hybridisation: sp3
7.10.3 GEOMETRY OF FOUR-COORDINATED iii. Geometry: Tetrahedral
COMPLEXES
iv. Number of unpaired electrons = 2
In these complexes, the coordination number of central atom/ion is
four. Such complexes may have either square planar or tetrahedral v. Paramagnetic

geometry, depending on whether the central atom/ion is dsp2 or vi. #s = JZ7ZizJ = 2.838 B.M.
sp3 hybridised. According to Pauling's prediction, if the complex
NDte:
is paramagnetic it should have tetrahedral geometry, whereas for
i. Tins the coordinafron entities [Ni(CN)4]2~ and [NI(Cl)4]2-
diamagnetic complex it should be square planar.
illustrate the useful rule originally called "the magnedc
Some of the examples are as follows:
criteriaofbondtype".Thatis,thegeometryofacoordinated
1. [Ni(CN)4]2-ion: Oxidation state of Ni in INi(CN)4]2-ion
entity can be predicted if its magnetic propertieE are
-+2
Ni atom in zero oxidation state/ground state has a
}=ivhiofa::oV:::::£Sihe#°go:I;:ewx:}!:::ice:}£:I:xf
Configuration of 3d8 4s2. is diamagnetic then its shape will be "square planar' and
Ni atom (3d8 4s2)
if it is paramagnetic then its shape be
ii. The above generalisation ofvB theory is not aapurate and
Ni2+ ion (3#) is one of its draw backs.
 Coordination compounds 7.53

3. [Ni(CO)4]: Oxidation state of Ni in INi(CO)4] is zero. Huggin suggested that [C:u(NHS)4]2+ has square planar
Magnetic measurements reveal that the complex is geometry,unpairelectroninCu2+resides
diamagnetic. 2+in[cuquH3)4]2+is
as shown

Ni atom (3d8 452)

3d 4s 4p .
Ill
Eun
sp3 hybridisa-tion
by 4 C0 1igands

Ni in [Ni(CO)4] undergoes sp3 hybridisation and hence

[Ni(CO)4] has tetrahedral geometry. In this example, isparamagneticwithone
Paulings's prediction that if the complex is diamagnetic,
it should have square planar geometry but it was found to 5. [Ni(ding)2] molecule: Oxidation state of Ni in [Ni (ding)2]
have tetrahedral geometry. is + 2.
3d 4s4p
i. The CO ligand is a strong ligand, so pairing of e-'s in
2-half-filled 3d orbitals occurs from 4s orbitals.
Ni atom (3d8 4s2)
ELun
ii. Hybridisation: sp3
Ni2+ ion (3d8)
mm
iii. Geometry: Tetrahedral
iv. Diamagnetic
Ni2+ in [Ni(din8)2] EEH
V. #s=zeroBM dsp2 hybridisation

4. [CuOTH3)4|2+: Coordination number ofcu2+ in [Cu(NH3)4]2+ i. The (ding) is a strong ligand so pairing of one electron
is four. Hence according to VBT, its geometry can be in 2-half-filled 3cJ orbitals occurs.
square planar or tetrahedral. Magnetic measurements have ii. Hybridisation: cJsp2 iii. Geometry: Square planar
predicted this complex to be square planar. iv. Number of unpaired electron = zero
3d
fi rfu v. Diamagnetic vi. #s = zero BM
Cu (3cJ[° ds])

cu2+ (3#) lm
tt
sp3 dybridisation
6. [CoC14]2-: Oxidation state of co in [CoC14]2-is + 2.

Co atom (3c77 4s2)

3d
Hm
4s4p

For [Cu(NH3)4]2+ to have square planar, Pauling predicted

Co2+ ion (3cJ7 4s°)
Em
a promotion of an electron from 3d to 4p. Making available
one 3d orbital.
Co2+ in [CoC14]2-
Hill
3d ds4p sp3 hybridisation (four elec-

EEH tron pairs donated by 4 Cl®

ions, forming tetrahedral
dsp2 hybridisation geometry
i. Hybridisation: c7sp2 i. C1°being weak ligand is unable to force the pairing of
ii. Geometry: Square planar electrons.
iii. Number of unpaired electron = 1 ii. Hybridisation: Sp3

[Link]--|Trfu>=j53-_1.732BM iii. Geometry: Tetrahedral

iv. Number of unpaired electrons = 3
v. Paranagnetic
[Link]--jTrfu]-_jTis=3.g]B.M.
7. [Zn(NH3)4]2+: Oxidation state of zn in complex = + 2.
3d 4s 4p
Zn atom (3d[° 4s2) Hun
Zn2+ ion (3cZ}°) Dill
7.54 Inorganic chemistry

[ZnovH3)4]2+ E]EH
^^
Em
tt
sp3 4 pair sp3 4 pair of
of electrous electrous
donated
by 4NH3 £°BT8#gbids.
ligand. If the geomerty of the
i. Hybridisation: sp3 If the pairing of electrons in the five half-filled 3d orbitals
ii. Geometry: Tetrahedral
iii. Number of unpaired electron = 0
iv. Diamagnetic
occurs.

[MnBr4]2-
+A
Em
dsp2
V. #s=zeroBM
The number of unpaired electron in the complex should be
8. [Pt(NH3)2C12] :Oxidation state of Pt in the complex = + 2.
4s6p
5d
mm :sq:::tg°i:::..E°e#Ses#r:db£:aet:::[£ts°n#ds=p3.::t:p¥.Whlch

lm
Pt atom (5d8 6s2)

pt2+ ion (5cZ8)

[PtovH3)2C]2]
+A
E] Fill
dsp2, 4 pair of
electrous donated Eu:rxefdpa[ti°:S:aet:£:tp;I;s[pP2tch[;|2r-1::sna:£So:[Link]:::is]r5e#[::;
by2NH3and2C|° the availability of one c7-orbital, pairing of electrons takes place
ligands in the remaining c7-orbitals. Hence there should be no unpaired
electrons in [Ptc14]2-ion.
i. NH3 being a strong ligand forees pairing ofelectrous of
2 half-filled 5drorditals. Pt (Z = 78) 3 5d8 6s2, Pt2+ 5 5d8.
5d
ii. Hybridisation: cZsp2
E] rfu
lm
pt" (Sdi 6sO 6pO)
iii. Geometry: Square planar
iv. Number of unpaired electron = 0 [ptcl4]2-
iv. Diamagnetic 4t
V. #s=zeroBM dsp2
SinceC1°beingweakligand,sopairingof3c7electrousshould
not occur, but for square planar complex (d sp2 hybridisation,
} moment value of [MnBrd2-ion is 5.9 pairing of electrous in 2 half-filled 5d orditals occurs.
Tpredictthetrybridisationandgeomerry It is a limitation of VB theory.

7.10.4 GEOMETRY OF SIX-COORDINATED

i sul.. , Oxidation state of Mn is the complex = +2. Since the COMPLEXES
6-6b;6ination number of Mn+2 ion in the complex = 4. Valence bond theory explains the formation of 6-coordinate
Therefore it will be either tetrahedral (sp3 hybridisation) or octahedral coordination entities by involving the use of
square planar (cJsp2 hybridisation). (# _ 1) c72 #s #p3 or 7!s xp3 #d2 hybrid orbitals by the central atom/
But the fact that the magnetic moment of the complex is 5 .9 BM
(given), which corresponds to # (number of unpaired electrons) :°nnse`:df:e:jnfs%8nodrss;3#£}:r[££dg£::f]So;.:.[Link]n¥:`[:teo°::::
-5. Octahedralcomplexesinwhichthecentralatomisczsp3hybridised
Due to the presence of 5 unpaired electrons in the 3d orbitals of
Mn+2, it should be tetrahedral in shape rather than square planar.
:oemc3::exdei::e;-h::Eftth[Link]trh[Link]if:s:;3';Z'h#i£?eed°:t:::#ea:
outer orbital octahedral complexes as shown below.
If the geometry of the complex lan ls
This distinction between inner and outer orbital complex is

|m
Mn (Z = 25), 3 3c75 4s2 based purely on magnetic measurements.
3d[(i.e. (#-1)d] 4r 4p 4d [i.e. „d]
Mn+2 3 3d5
Since Br® is a weak ligand so pairing of electrons in the five
half-filled 3d orbitals will not occur.
d2sp3 hybridisation

Mn+2(3d5)
3d
Iud
4s4p
(irmer orbital or
spin paired or low spin) complex
 Coordination compounds 7.55

3d [(i.e. (#-1)cH

|m
4$ 4p

sp2c72 hybridisation
4d [i.e. #cfl vi. Diamagnetic 4s = zero BM
3. [Co(CN)6]4-(hexacyanocobalt(II) ion): [Co(CN)6]4-ion is
paramagnetic corresponding to the presence of one unpaired
electron.
3d 4s 4p 5s
(outer orbital or
spin free or high spin) Co atom (3cZ7 4s2 4p°)
mmE
complex
Co2+ ion (3d7 4s° 4p°)
HmE
7.10.5 ` SOME EXAMPLES OF INNER ORBITAL
COMPLEXES Co2+ in [Co(CN)6]4- E ill H
1.:::f%)#±:::iy[Link];:atthea(#i£!sorTo):#neet];nspfua:r£:: c72xp3 hybridisation

electron and hence paramagnetic. Thevalenceshellelectronicconfigurationofco2+ioninfree

3d 4s 4p state is (3cJ7 4s° 4p° 5s°), in the complex ion, [Co(CN)6]2-
Fe atom (3c* 4s2 4p°)
mm electronic configuration is 3cf 4s° 4p° 5sL .

Fe3+ ion (3d5 4s° 4p°)

uor lm
Fe3+ in [Fe(CN)6]3- EEH
t #xp3 hybridisation t
The presence of unpaired electron in 5s is supported by the
fact that since 5s orbital is of high energy, the one unpaired
electron residing in it should be unstable and hence should
i. CN°being a strong ligand force pairing of5-half filled be easily lost. Experimentally it has been found to be true.
3d orbitals
[Co2+L6]4--[Co3+L6]3-+e®
ii. Hybridisation: d2sp3
When [CoL6]4- is acted upon by air or H202, the complex
iii. Geometry: Octahedral
easilygetsoxidisedto[CoL6]3-,therebylosingtheunpaired
iv. Inner orbital or low spin or spin paired complex. electron present in 5s orbital.
v. Number ofunpaired electron = 1 Thus we conclude that Co2+ inner orbital octahedral
vi. Paramagnetic complexes are unstable (or labile) and hence gets easily
Vii. #s= J5 = 1.732 BM oxidised to Co3+ complexes by air or H202. Consequently,
such complexes should be prepared in an inert atmosphere.
2. [Fe(CN)6]4-ion (hexacyanoferrate(II) ion): Magnetic
studiesof[Fe(CN)6]4~ionhaveshownthatthiscomplexion 4. [Coav02)6]3-(hexanitrito-N-cobaltate(III) ion) :
is diamagnetic, i.e. number of unpaired electron on central Magnetic studies reveal that the given complex is
metal ion is zero (# = 0). diagmagnetic (# = 0).
3d 4s 4p 3d 4f4p
mm Co atom (3d7 4s2 4p°) mum
lm
Fe atom (3d6 4s2 4p°)

Fe2+ ion (3d5 4s° 4p°)

tytyRy lm Co3+ ion (3cf 4s° 4p°)

Co3+ in [Co(N02)6]3-
Eun
Fe2+ in [Fe(CN)6]4-
t
E]un
d2xpJ hybridisatiofl t
d2xp3 hybridisation

Since the complex is diamagnetic, all the electrons in

3d-orbital gets paired up.
It is due to d2sp3 hybridisation that [Fe(CN)6]4- is an inner
i. N02°being a strong ligand forces pairing of4 half-filled
orbital octahedral complex. The electron pair donated by
3d orbitals.
CN° ion (1igand) is accommodated in each of the six #sp3
hybrid orbital as shown above. ii. Hybridisation: c}2sp3
i. CN© being a strong ligand force pairing of4 half-filled iii. Geometry: Octahedral
3cJ orbitals
iv. Inner orbital or spin paired or low spin complex.
ii. Hybridisation: d2sp3
v. Number ofunpaired electron = 0
iii. Geometry: Octahedral
iv. Inner orbital or low spin or spin paired complex. vi. Diamagnetic
v. Number ofunpaired electron = 0 vii. „s - 0
7.56 Inorganic chemistry

Note: Oxalate, generally behaves as weak field ligand but with Note:[Fe(NO)(H20)5]2+ionisformedinthebrownringtestfor
CQ(cobalt), it behaves as a sriong field ligand like NH3 e.g., in the confirmation of nitrate ion in the salt analysis. To the nitrate
the compound [Co(OX)3]3~. solution, equal volume of fresmy prepared saturated solution of

[Link] Some Examples of Outer Orbital

Octahedral Complexes
1. [FeF6|3- ion (hexafluoridoferrateall) ion): In [FeF6]3-,
CNofFeissix,hence[FeF6]3-ionhasoctahedralgeometry.
Oxidation state of Fe in [FeF6]3~ is +3.
3d 4d
Featom(3rf
4s2 4pO 4J)) IonicequationsforNQ3©iontestis

Fe3+ atom
(3dr5 4po 4di)
EEIH
4t
4H® + See + ira - + NO + 2H
sp3# hybridisation
There are five unpaired electrons and hence # = 5. Magnetic

¥rh°ep:It;e;.::;:tar[esv:sa:dt?:ts£F;2F£]y3;ni:]Fsafts;opna::em4ad:eat:Cd
4dx2_,2 and not 3dz2 and 3dx2_,2. 3. [Ni(NH3)6]2+ ion (hexaamminenickelate(II) ion :

i. F®being aweak ligand is unable to pair 5 half-filled 3d INi(N113)6]2+ionCNofNiissix,henceINi(N113)6]2+ionhas

electrons. octahedral geometry. Oxidation state of Ni in [Ni(NH3)6]2+
ion is +2.
ii. Hybridisation: sp3cP
3d 4d
iii. Geometry: Octahedral
iv. Outer orbital or spin free or high spin complex.
Niatom(3d8
4s2 4p° 4Of )
ffi ffi
v. Number ofunpaired electrons = 5
vi. Paramagnetic
Ni2+ ion (3d8
4sO 4pO 4di)
lm
vil] . ps= Ji6Fii) = J5is = 5 .92 f"
2. [Fe(NO)(H20)s]2+ ion
INiqu3,6,2+ EEH
tt
(pentaaquanitrosoniumiron(I) ion) : sp3d2 kybrid
ofoitals. 6 pair of
[Fe®avo)®(H20)5]2+ ion CN of Fe is six, hence it has
electrous denated
octahedral geometry. Oxidation state of Fe in
by 6NH3 tigands
[Feovo) (H20)5]2+ ion is +i.
3d 4d Note: With most of the central metalfion, behaves as a
Featom(3d6
strong ligand but with some metavion e \\-'i-:-ion, it behaves
4st 4po 4drJ>
eck ligand.
Fee ion (3d6
4sl4pO4#)

Fee ion in
E- Hm
EEH
one of its drawb
i.
accurate and ig

In the above complex NH3 being weak ligand is not able

to force pairing of electrons.
ii. Hybridisation: sp3c72
(¥dT4;tpr2°)5]2+ tp3#hybridisation^ iii. Geometry: Octahedral

iL NO© is a strong ligand so forces the pairing ofouly one iv. Outer orbital or spin free or high spin complex.
unpaired 3s electron to one half-filled ofoital of 3d. v. Number ofunpaired electrons = 2
EL Hybridisation: sp3d2 vi. Paramagnetic
iii. Geometry: Octahedral [Link]--jrfu>-_ji8=2`83BM
iv. Outer orbital complex. 4. [Cr(NH3)6]3+ (Hexaaminechromium(Ill) ion):
v. Number ofunpaired electrous = 3 Oxidation state of Cr = +3, coordination number (CN) of
vi. Paramagnetic Cr3+ ion = 6.
vii. #s = JB = 3.83 BM Valence elect`ronic configuration of:
Cr atom i 3d5 4st, Cr3+ ion = 3d3
 Coordination compounds 7.57

3d 4s 4p
Cr atom Co atom

cr3+ ion co3+ ion

[CrQVH3)6]3+ ion [CoF6]3~ ion

tt
c72sj73 hybrid orbitals. 6 sp3d2 hybrid
pair of electrons donated ofoitals. 6 pair of
by 6 NH3 ligands. electrous donated
by 6F° ligands
i. Hybridisation: d2sp3 ii. Geometry: Octahedral

iii. Inner orbital or spin paired or low spin complex. i. F°being a weak ligand is not able to foree pairing of
electrous.
iv. Number of unpaired electron = 3
ii. Hybridisation: xp3d2
v. Paramagnetic
iii. Gcometry: Octahedral
vE. ps-= Ji6Tf y) = JTi5 = 3.281 fIM
iv. Outer ordital or spin free or high spin complex.
5. [CoF6]3-alexafluoridocobaltateall) ion) : Oxidation state v. Number ofunpaired electrous = 4
of Co = +3, coordination number (CN) of Co3+ ion = 6.
vi. Paramagnetic
Valence electronic configuration of:
Vii. #s= JZ7ZTZJ=JZZ = 4.90 BM
Co atom 3 3c77 4s2, Co3+ ion = 3crf .

Table 7.17 Geometry (shape) hybridisation and magnetic nature of some of the complexes (application of valence bond
theory)

Atom/ioncamp,ex Configuration
i ed\693 S^ a` xifes;|RE
.,oxidatiinstateof;i:;ltletal,:r:I

3¢otsex¥ga`§o

1 2 3 4 5 6 7
A
sc3`(#)[scF6]3- 3d ds fry +3+3 0o DiamagneticDianagnetic
1111 llm
Ill:I:I E ill d2sp3(irmer) Octahedral
4+
dzxpJ

'8
Ti3+(dl)[TiF6]3-[Ti(H20)6]3- 3d 4$ 4p +3+3+3 ParanagneticParamagneticParamagnetic
11111 Ibm
111 I:I:lE EH d2£p3(inner)d2sp3 OctahedralOctahedral 11

tt
`1-``[`-`

11 I I:I:I E ill
A+ (irme'r)
disp3

Ti4+(#) +4+4 DiamagneticDiamagnetic

11111 lEm 0-0

[Tix6,2- I Ill:I:I E Elm d2#p3 Octahedral

+A (inner)
dzspj
 C
v3+(d2)[V(H20)6]3+ 3d ds 4p +3+3 22 ParamagneticParamagnetic
111111 lEm
11111:I:I E ill d2Sp3 Octahedral
t1 (irmer)
d2xpj
D
cr3+ (d3)[Cr(H20)6]3+[CrquH3)6]3+[Cr(CN)6]3-[crF6,3-[crorH3)4cl2]® 3 cJ 4$ 4p +3+3+3+3+3+3 333 ParamagneticParamagneticParamagneticParanagneticParamagncticParamagnetic
111111111 in
OctahedralOctahedralOctakedralOctchedralOctahedral
iiiiii:I:I E un d2sp3
t4 (irmer)d2sp3(in er)rfsp3(imer)#sj,3(irmer)
dzsp3

1[1111:I:I E in
+4
dzspj
111111:I:I E EH
44
-``1,`

iii]ii :I :I E rm
+4
dzsp3
d2sp3(imer)
1 I 1 I 1 I : I : I E ill
t4
d2sp3
cro(rfu[)[Cr(cO)6] 3d 4s 4p 4d 00 50 ParanagneticDiamagnetic
iiiiiiiiHH mi I I I I I
1LllLlll:I:I E EH 1111 I I d2xp3 Octahedral
t4 (imer)
d25P3

cr2+(#)[Cr(CN)6]4-[Cr(H20)6]2+[crorH3)6]2+ 3d ds 4p 4d +2+2+2+2 4044 ParamagneticDiamagneticParamagneticParamagnetic

iiiiiiii iE mi I I I I I
d2sp3(irmer)sp3d2(outer)sj,3¢2(outer) OctahedralOctchedralOctahedral
1LllLl I:I:1E EHl I 1111
t^
d2sp3

11111[11 lE EIHl:I:I Ill

+1.
Sp3d2

11111111 lE EHl:I:I Ill

t1
sp3d2
E
Mn+t(3cJ54s[)[Mp(CN)6]5- 3d 4$ 4p +1+1 6`0 ParamagneticDiamagnctic
1 I 1 I 1 I 1 I 1 I ill ill
d2sp3(inner) Octahedral
iLiiLiiLI : I :I E un
A+
d2sp3
 Coordination compounds 7.59

Mn+2 (3d5)[Mn(CN)6]4-[Mnc14]2-[MnBr4]2~[Mn(H20)6]2+ 3d 4s 4p +2+2+2+2+2 51555 ParamagneticParamagneticParamagnetieParamagneticParamagnetic

1 I 1 I 1 I 1 I 1 I I ill
d2xp3(irmer) OctahedralTetrahedralTetrahedralOctahedral
i}mli I : I :I E RE
44
• d2Sp3
3
JPsp3sp3d2(outer)
I 1 I 1 I 1 I 1 I 1 I +E EIH+

JP 3

1 I 1 I 1 I 1 I 1 I I Elm
t4
sp3
3d 4$ 4p 4d
||111111]114E ill':I:i I I I

sp3d2
Mn3+(3#)[MnF6]3-[Mn(acac)3]°[Mn(cN)6r 3d ds 4p +3+3+3+3 4440 ParamagneticParamagneticParamagneticDiamagnetic
111111111 I ill
3d ds 4 4d
`1;``,.``(outer)sp3d2(outer) OctahedralOct'ahedralOctahedral
111111111 : : : : I:I:1111

t^
fp3d2
3a 4s 4P 4d
111111111 IF EHl:I:i I I I

JP3cZ
sp3d2(irmer)
1LllLl I:I:I E EH
+A
d2£p3

F
Fe(3d6452)Fe(CO)5 3d 4s 4p 00 40 ParamagnetieDiamagnetie
iLli li ii ii I in in
1LllLllHILI : I E RE dsp3(imer) Trigonal
t4 bipyramidal
dsp3
Fee(3d64fl)[Fe(H2o)5oro)]2+ 3d 4s 4P 4d +1+I 53 ParanagneticParamagnetic
11'111111111 ill ill Ill I 1111L[1LIlllllI+EEHI:I:i111
Sp3d2(outer) Octahedral

•rirf
`44404
Fe2+(3d6)[FeorH3)6]2+Fee(H20)6]2+[Fe(cN)6r[Fec14,2- 3d ds 4p 4d +2+2+2+2+2 ParanagneticParamagnetic,ParamagnedcDiamagnetieParamagnetic
1Llllllllll I ill Ill I I I
`lf`,`-(outer)sp3d2(outer)d2gp3(irmer) OctahedralOctahedralOctahedralTetrahedral
1Llllll1]1IE EHl:I:I Ill
+4
Sp3d2

]1LllllllIlltE EHl:I:i I 11
sp3d2

1L]1LIlll : I : I I EH
tt
d2sp3
sp3
11L111111I114ERE4
3
SP
Fe3+(3d5)
iiiiiililiiE mi I I I I I
+3+3+3 - 5 Paramagnetic

sp3d2(Outer)sp3d2(outer) OctaledralOctahedral 55 ParamagnetieParanagnetic

[Feor2o)6]3+[FeF6]3- 11]1111111lE EIHl:I:I I I I
+,4
sp3d2

111111111lE REl:I:I Ill

4t
Sp3d2

[Fe(CN)6]3-[Fec14]© +3+3 d2sp3(inner)sp3 OctahedralTetrahedral 15 ParamagneticParamagnetic

11L[1L[11 : I : I H Elmt4`d2sp3

1 I 1 I 1 I 1 I 1 I E ill
A+
sj,3

G
co2+ (dfl)[CO(H20)g]2+[cocl4]2- +2+2+2 333 ParamagncticParamagnetieParamagnetic
11L[1Ll 1 I 1 I 11 I ill

1L!1Llllllll : : : : I:I:1111
sp3d2 octaledralTetrahedral
A+ (Outer)xp3
sp3d2

1LllLl1 I 111 I E ill

tt
sp3

[co(cN,6,4-[cooro2)6]4~ 3d ds 4p 5s +2+2 d2sp3 OctahedralOctahedral 1e- ParamagneticParamagnetic

1LllLllLl:I:I : : : : 1 (inner)d25P3(irmer) (in 5s
t4` Orbital)1e_(in5s
d2sp3
3d 4f 4p 5s
1LIIHIL1 : I : I E RE H
A,t
orbital)
d2sp3
!co3+(giv +3+3 40 ParamagneticDiamagnetic
iiL[i ii I 1 ii I I in
[coorH3>6]3+ llLllLllLI : I : I E EH d2sp3 Octahedral
A+ (inner)
*2sj,3

Note: NHS acts as wgak ligand for Co+2 and strong ligand for Co" ion.
[C0IN02}6]3-[CO(CN)6]3-[coF6,3- +3+3+3 d2xp3(irmer)d2xp3(irmer)d2xp3(Outer) OctahedralOctahedralOctahedral 004 DianagneticDianagneticParanagnetic
1LllLllLl : I : I E] RE
14
d2sp3
1LllLllLI :I : I E EH
+4L
#sp3
1LlllllllllE EHl.:I:I I I I
4.1
sp3#
H

ce
Ni(3#4J2)Ni(CO)4 00 20 ParamagneticDianagnetic
iLiiLiiLi 1 ii I H in

|1LllLllLllLllLI F REt Sp3 Tetrahedral

3
SP
 Coordination compounds 7.61

Ni2+(d8)
1LllL]1Ll 1111 I ill
+2 - - 2 Paramagnetic

INiqull3,6,2+INic,4,2-INi(CN)4]2-INi(din8)2]INi(bigH,2]2+givfquH3)4]2+ +2+2+2.+2+2+2 sp3d2(Outer)xp3dxp2dfp2dxp2£p3 OctahedralTetrahedralSquareplanarSquare`planar 2 0 02 ParamagneticParamagneticDiamagnetieDiamagneticDiamagnetic•Dianagnetic

11lllL]1lIllll+E ill I:I:11 I IAsp3d2

1LIllllLl 1111 H RE
+A
fp 3
iLiiLiiLliLi : I E in
tt
dy,I
1LllLllLwl : I E qu
+A
dsp2
SquareplanarTetrahedral
1LllLllLllLl : I E ill
A.+
dsp2

1LllLllLl 1111 E RE
+A
sp3
I
Ou2+(di)[CuC14]2-[cuQun3)4]2+ +2+2+2 1i1 Paramagnetic
11L]1LllLllLll I I ill

Sp3chj,2 TetrchedralSquareplanar ParamagneticParamagnede

11LllLllLllL[1 I E EH
+
JP 3

1L[1LllLIIL] : I E RE
t+
dsp2
•mentally d, 2`:
ete ruined), ana hEnee dspr
gy®£:d!:eudqB¥;)a::+o:;ixgp:oct£::%;bn::tp£3s#g£;S:£db£:;t[£::gfe)£]t2o+;Se:3¥:.P{[o¥3¥p(:£Xnie4;
[Cu(CN)4]2- +21 xp3 Tetrahedral 1 Paramagnetic
1LllLllLllLll I E EH
++
sp3
cue (dlo) +i - 0 Diamagnetic
iiLmiiLiiLilLi I ill
+I sp3 Tetrahedral 0 Diamagnetic
[Cu(CN)d3- WIILllLllLllLI E RE
Sp3

J
zn2+(c'10) 00 00 DianagneticDiamagnetic
11lllLllLllL]1ll I ill I I I I I I

[znour3)6]2+in llLllLllLllLllLI E EH I:I:1111 xp3d2 Octahedral

crystal only +A (Outer)
`lf`,`-

7.10.6 LIMITATIONS OF VBT properties including the magnitude of orbital contribution

to the magnetic moments, e.g. both tetrahedral (sp3
While the valence bond theory to a large extent explains the
hybridisation) and outer orbital octahedral (xp3d2
formation, structure and magnetic behaviour of coordination
hybridisation) complexes of Co(+2) (cJ7 system) have
compounds, it suffers from the following shortcomings :
three unpaired electrons and are therefore expected to have
1. .VBT fails to explain the finer details of magnetic
#s = 3.87 BM. The tetrahedral complexes have generally
7.62 Inorganic chemistry

#s = value in the range of4.44.8 BM, while the octahedral

complexes have #s in the range of4.7-5 .2 BM VBT cannot
explain the increase in value of #s. Magnetic momeflt value of ion in 3
2. It does not explain the variation of magnetic properties of Find out the oxidation state of iron and type of
complex with temperature.
RERE #s = 3.89 BM corresponds to # = 3.
3. The magnetic moment values of complexes of certain ions
Take 3.89 g3 4 3 Jig a J13 B.M.
(e.g. Co2+, Ni2+ etc.) are much higher than those expected
by spin only formula. VBT cannot explain the enhanced The value J13 BM corresponds to # = 3.
values of magnetic moment.
The oxidation state of Fe in the complex.
4. VBT cannot inteapret the spectra (color) of the complexes.
5. VBT cannot explain as to why Cu2+ forms only distorted [Fe+1(H20)5#O]2+is+1andcNofFe®=6
octahedral complexes even when all the six ligands are Fe(Z=26)33d6452, Fe®=3d645]
identical.
3d4s 4d
6. It does not make exact predictions regarding the tetrahedral
and square planar structures of 4-coordinate complexes.
Fe© (3d6 4s]) ill EH
7. It does not give a quantitative interpretation of the SinceNO®isastrongligandandH20isaweakligandsoonly
thermodynamic or kinetic stabilities of the coordination one pairing of 3d and 4s electrons occurs which also corresponds
compounds. to „ -3.
3d 4s 4 4d
8. It does not explain why in some complexes, metal ion
forms inner orbital complex (c}2sp3, low spin complexes) [Fe©(H20)5NO]2+
whereas others form outer orbital complexes (sp3d2, high ("-3) A A
sp3d2 hybridisation
spin complexes).
9. It does not distinguish between strong and weak ligands. i. Oxidation state of Fe = +1
ii. Hybridisation = sp3c¢
iii. Gcometry = octahedral
iv. Outer ordital complex.

RERE #s = 2.8 BM corresponds to # = 2.

The differences between inner orbital and outer orbital

octahedral complexes have been given in the following table:
Inner orbital` arfer #+^bREl
Thus Mn in [Mn(CN)6]3- has two unpaired electrons (# = 2). + i octahedral cornplexes a ctahedral complexes +
Oxidation state of Mn in [Mn(CN)6]3-is +3, Mn (Z = 25) I, The octahedral i. The octahedral
3 3d54s2 and Mn+3 = 3# hybridisation used in hybridisation used in

Mn3+ (3#)

Mn3+ ion in
lm
u- Hill
3d 4s4p the structre of these
complexes involves
the use of two (7z -I)
d, one ns and three
the structure of these
complexes involve s
the use of one ns,
three 73p and two riJ
#p orbitals. In case orbitals. In case of
[Mn(CN)6]3- t J2xpJ t of 3d-block elements 3cZ~block elements
this hybridisation is this hybridisation is
i. CN©being a strong ligand, forces only one pairing of represented as (3d)2 represented as (4s)
4 half-filled 3c7 orbitals. (4s) (4p)3 or simply (4p)3 (4cD2 or simply
d2sp3 asfp3d2
Remember:
i, haattypeeleetruni On, nopairingocc ether ii. These complexes ii. These complexes are
the ligand |S strong Qr weak. are given by strong given by weak ligands
ii. In # type electronic corfuguration, only one p ligands

the nls d2sp3 with edral geometry+

iv. Irm€r orbital complex.
 Coordination compounds 7.63

iii. In these complexes iii. In these complexes are diamagnetic while [CoF6]3~ and [Co(H20)6]3+ are
strong ligands force weak ligands are paramagnetic.
the metal d-electrons not able to pair up 5. Consider the following complex compounds.
to pair up and hence d~electrons and hence tl) [ptoJH3)4] [ptoro2)4]
these complexes the valence shell
(11) [CO(H20)6] [COBr6]
generally have configuration of the
(IID [Cr(H20)5 0V02)] [Pt (CN)4]
paired elections metal in the free state
If cz, a, c are more possible coordination isomers of given
(diamagnetic) or and in the complex
complex compounds respectively then calculate the value
lesser number remains the same.
of a + b + c.
ofunpaired Thus these complexes
6. Consider the following complex compounds.
electrons (wealELy generally have larger
paramagnetic) number of unpaired (I) [Pt(H20)2(CNS)2]
electrons (strongly ¢1) [Co(CN)2Br2]2-
paramagnetic) all) [cr(e#)2cl2]®
iv. These complexes are iv. These complexes are (rv) [Cro{H3)3Br3]
also called low spin also called high spin
0 [Rh(en)3]3+
complexes complexes
rvD [Pt(e#)(CN)2]
Calculate the sum total of geometrical isomers in all
above compounds.
7. Total number of geometrical isomers of
+4-I-1-1 -I 0
[ptBrci I (cN)(H20)(Nfr3)]2+complex ion, is x
and total number. of geometrical isomers of the above
ffiHffiB [ZnBr4]2-oxidation state of zn is +2. compound when all the 'halide ions are in cis position is )/
Electronic configuration of zn (Z = 30) = 3cJ]°4s2 then the value of (x + y) is
= zn2+ - 3d`0 8. For the complex compound [Cu(H20)4] [PtBr4] if X is

Zn2+ ion (3c7]°)

zn2+ ion in
3d
lm
4s4p

Hill
the number of more coordination isomers and for the
compound [Cr(gly)(e#)2]2+ if y is the number of stereo-
isomers, then (x + y) is
9. Total number of complex compound among the following
[ZnBr4]2- tt which are optically active?
sp3
a) [CO(OX)3]3~
Since the cJ-orbitals are completely filled, there are no unpaired (11, [Ru(dipy,3]3+
electrons.
(Ill) cis - [Cr(N02)3(H20)3]
(IV) cis - [Cr(CN)3 (dien)]
rv) trams - [Cr(CN)3 (dien)]
1. On the basis ofvBT, answer the following complexLeions: rvl) cis - [Rh Br2(H2o)4]®
I. [Ti(bpy)3]° II. [V(H20)6]3+ rvll) [pt(cN)2(en)]
Ill. [Mn(CN)6]4- IV. [Mn(CN)6]3- 10. Total number of possible optically active isomers in
complex compound (I) and (11) are:
V. [IrQ{H3)6]3+
(I) [Mo Br2 12 (Sly)]-I
a. Type of hybridisation involved. (11) [Cr CIBrl OrH3) (en)]
b. Type of inner or outer orbital octahedral complex. 11. Find out the total number of optically active isomers
c. Magnetic behaviour and #sp±n value. for complex compound having molecular formula Pt x
2. Identify the complexes which are coloured and which are (en)Br4, where (x = 1, 2, 3)
colourless. Explain. 12. The following compounds are given:
a. [craun3)5 qucs)] [zncl4] (I, [Pt C14r2
b. [Tioro3)4] c. [cuorc-cH3>4]© BFg (II) IF4®
all) [Mn (H2o)6]2+
d. [Cr(NI13)6]3+3Cl® e.K3[VF6]
(IV) IF7
3. Write the IUPAC nomenclature of the given complex If cz is the total number of axial d-orbitals having zero
along with its hybridisation and structure. nodal plane, a and c are total number of non-axial and
Ca[Croro) (NH3) (CN)4], #spjn = 1.73 BM axial cJ-orbitals respectively, each one having two nodal
4. On the basis of CFT, explain the following complexes of planes used in hybridisation of centrals of compounds I to
Co3+ like [Co(NH3)6]3+, [Co(en)3]3+ and [CoO{02)6]3- IV.
7.64 Inorganic chemistry

Calculate the value of a + b + c. ); = Total number of electrons in non-axial d-orbitals of

13. Consider the following transformation inner shell of central metal ion in the complex Co(ding)2.
Cr(CO)x - Cr(CO)y quo)z Then calculate the value of (x + y).
If both reactant and product follow BAN rule, then 22. Consider the following transformation.
calculate the value of x -ty + z). [:p°Li¥c2o3}fe!;3fr[cociy]w
14. Consider the following ligands: Blue complex

(1) acac (2) Phen Find the value of a + )J - 7z).

(3) DMG (4) 02-
(5) N02- (6) NH2©
. (7) OHO (8) Gly
7.11 CRYSTAL FIELDTHEORY
(9) C032- (10) en Crystal field theory is now much more widely accepted than the
valence bond theory (VBT). This theory was proposed by Bathe
(11) s042r (12) cH3coo®
and Van Vleck in 1930 and popularised by Orgel in 1952. CFT
If a = Total number of flexidentate ligands
is an electrostatic model which considers the metal ligand bond
b = Total number of ligands which acts as bridging as
well as monodentate only (M + L) to be ionic arising purely from electrostatic interaction
between the metal ion and the ligand. Ligands are treated as point
c = Total number of unsymmetrical bidentate ligands
charges in case of anions or dipoles in case of neutral molecules
d = Total number of bidentate ligands only.
which have a Ions. pair of electrons. If the ligand is a neutral
Then calculate the value of (cz + b + c - dy)
molecule such as NH3 and H20:, the negative end of the dipole
15. loo mL of 0.2 M solution of CrBr3.ENH3 was treated
in the molecule is directed towards the metal ion. The electrons
with excess ofAgN03 solution and 0.04 moles ofAgBr is
of the central metal are under repulsive force from those of the
precipitated. The value of i is ligands. Thus the outermost electrons in the d-orbitals of central
2
transition metal atom/ion occupy those d-orbitals which are far
16. Find out the number of compound(s) in which at least away from the direction of approach of ligands.
half of Br® ions are ionizable.
In CFT, the following assumptions are made
a) cOBr3.6NH3 (ID CoBr3.5NH3 1. Ligands are treated as point charges.
¢ID CoBr3.4NH3 (IV) CoBr3.3NH3 2. There is no interaction between metal orbitals and ligand
rv) .ptBr4.6NH3 (VI) PtBr4.5NH3 orbitals.
orl) ptBr4.4NH3 rvlll) ptBr4.3NH3 3. The arrangement of the ligands around the central metal ion
(|X) PtBr4.2NI13 is such that the repulsion between these negative points is
17. Maximum numberr of N-atom that can lie in molecular minimum.
plane of the complex [M(trien)]2+. 4. Splitting of d-orbital energies: The five d-orbitals in an
18. Find out the total number of ionic species/compounds in isolated gaseous metal atom/ion, have same energy i.e. they
which central atom uses cJz2 orbitals in its hybridisation. are degenerate (as shown in Fig. 7.28). This degeneracy is
a) [cr(H2o)6]3+ (I,, Mn040 maintained if a spherically symmetrical field of negative
(Ill) [Pt l2qu3)2] (|V) Fe (CO)5 charges surrounds the metal atom/ion, but all of them will
rvj INi (cNs)4]2- IVI) [CrBr5]3~ be raised in energy as a result of repulsion between the
negative field and the elctrons in the orbitals.
IVII, Xe©F5 rvlll) ciF5
¢X) Ni (CO)4
19. Find out the total number of diamagnetic inner orbital
complexes.
(I) [Fe(H20)5NO]S04 (11) Ca[Fe(CNS)5NO]
(Ill) [CuQ¢H3)4]S203 (IV) Ca2[CO(CNS)6]
cO Na3[CO(OX)3] rvl) CaINiBr4] .
rvll) Na3 [Fe(CNS)6] rvlll) Na3 [cr(sNc)6]
(IX) Ca[Pt Br4]
20. If x = maximum number of C-atoms that lie in a plane.
y = Number of C-atoms which are Sp3 hybridised.
z = Number of C~atoms which are Sp2 hybridised.
3dry 3dxz .1`'`:
Then, find out the value of (x + )/ - 3) for the complex
Fig. 7.28 Spatial arrangement of five d-orbitals
[Ni(din8)2]
21. If x = Total number of electron(s) in axial d-orbitals of However, when this negative field is due to ligands (either
irmershellofcentralatomioninthecomplex[Co(CN)6]3 anions or the negative ends of dipolar molecules like NH3
 Coordination compounds 7.65

and H26:) in a complex, it becomes asymmetrical and the

degeneracy of the d-orbitals is lifted. It results in the splitting
of the d-orbitals. The pattern of splitting depends upon the
nature of the crystal field. It is this splitting of cJ-orbital
energies and its effects that forms the basis of crystal field
theory.
In most transition metal complexes, either six or four
ligands suround the metal, giving octahedral or tetrahedral
structures. In both of these cases the field produced by the
ligands is not spherically symmetrical thus the d-orbitals
are not affected equally by the ligand field. Free metal ion
(Five degenerate
d orbitals)
7.11.1 CRYSTAL FIELD SPLITTING OF d-ORBITALS IN
OCTAHEDRAL COMPLEXES Fig. 7.31 (a) Crystal field spLiffing of d-orbitaLs in an octahedral field

i. In an octahedral complex, the metal is at the centre of Thus, the degeneracy of the d-orbitals have been removed
the octahedron and the ligands are at the six comers. The due to ligand electron-metal electron repulsions in the
direction I, y and z point to three adjacent comers of the octahedral complex to yield three orbitals of lower energy,
octahedron as shown in Figure 7.29. f2g set and two orbitals of higher energy; eg set Fas shown
Z
in Figure 7.31 (a) and 7.31@)].
The lobes of the eg orbitals (c7x2_y2 and dz2) point along the
axesj¥,};andz.Thelobesofthef2gorbitals(dry,dxzanddyz)
point in between the axes. It follows that the approach of
the six ligands along the x, );, z, -x, -y and -z directions will
increasetheenergyoftheorbitalsdx2_,2anddz2(whichpoint
along the axes) much more than it increases the energy of
I thedry,dryanddyzorbitals(whichpointsbetweentheaxes).
+z
Fig. 7.29 Tl`e directions in an octaltedraL complex

ii. In octahedral coordination entity with six ligands surrounding

the metal atom/[Link], there will be repulsion between the
electrons in the metal d-orbitals and the electrons (or
negative charges) of the ligands. Such a repulsion is more
when the metal d-orbital is directed towards the ligand than

:r%:tnaifstish:cwhapyofn:roth:d]i8£:dk¥|S;n¥ethde*2d-£ecat::nd6i
the ligand will experience more repulsion and will be raised

:n[Link]gtfdatxh[:?#i[dgzea]:dw€¥e:rift:]nse¥£]Cr:[aa::vdefrt:C:::
average energy in the spherical crystal field (as shown in -Z
Figure 7.30).
Fig. 7.31 (b) Complete set of d-orl)itals in an octahedral produced by six
L€gandsihT:o:Zs°::i::Les;zr2eosrhb::a:Ldhaansdbteheent3gm:[Link]ra::a:njhaded.

<
C>
-ve clanged
Large
interaction
iii. This splitting of the degenerate levels due to the presence
of ligands in a definite geometry is temed as crystal field
ligand splitting (CFS) and the energy separation is denoted by Ao

d*2-J2
(the subscript 0 is for octahedral). Thus, the energy of the
twoegorbitalswillincreaseby(+oro.6)Aoandthat

i= `'m.
<

Fig. 7.30 Interaction of Ligands with d-orbitats

Small
interaction
ofthethreef2gwilldecreaseby(?oro.4)Ao.

To understand this splitting more clearly we can assume it

be to a two step process as shown in figure.
7.66 Inorganic chemistry

correct wavelength (energy) to promote the electron from

the f2g level to the eg level.
v. [Ti(H20)6]3+shows maximum absorption at 20,300 cm-1.
The value ofAo i.e. , "Crystal Field Splitting Energy" (CFSE)
for [Ti(H20)6]3+ can be calculated as
Average
energy level
(Bary or Ao=E=N#=NAhc-v
Barycentre)
= 6.023 x 1023 mor[ x 6.6 x io-34 Ts x 3 x io8 ms-1
'2g

x 20300 x |o2 in-l

= 241.97 x 103 J mol-I

= 242 kT morl
Fig. 7.32 d-orbitals splitting in an octahedral crystal [Link]
Because of the crystal field splitting of cJ-orbitals, the
Step 1: Average energy of the d-orbitals of metal atom/ion in a single d-electron in [Ti(H20)6]3+ occupies an energy level
hypothetical spherical crystal field. [Link]
Step 2: Splitting of d-orbitals of metal atom/ion in octahedra| the complex is more stable. The crystal field stabilisation
crystal field. energy; CFSE in this case is

In step I, the ligands approach the central metal, producing a CFSE = ~ 0.4 Ao = -0.4 x 242 kJ mol-I
hypothetical spherical field which repels all of the d-orbitals Ao=-96.8kJmol-I
to the same extent. In step 2, the ligands exert an octahedral
field, which splits the orbital degeneracy. In going from 7.11.2 SIGNIFICANCE OF Ao
step 1 to step 2, average energy (the barycentre or "centre Consider a d] coordination entity e.g. [Ti(H20)6]3+ formed in
ot gravity") of the orbitals must remain constant and thus, aqueous solution of Ti3+ (d[) ion, now the single d-electron
the two `eg' orbitals to be further repelled by 0.6 Ao while occupies one of the lower energy f2g orbitals. Similarly in the d2
the three `f2g' orbitals are stabilised to an extent of o.4 Ao as andd3coordinationentities,thed-electronswilloccupythelower
shown in figure 7.32. This constancy of the barycentre of the energyf2gorbitalinaccordancewiththeHund'[Link],
d-orbitals holds for all complexes, regardless of geometry. two possible pattern of electron distribution arise depending upon
the relative values of Ao and P, where P represents the energy
required for electron pairing in a single orbital called the pairing
energy.
a. If Ao < P (weak field, high spin situation): The fourth

;3:;C:¥£::;::[§;;:1::3:;o,en::fn;:o;:;:a;S:g§Ege±:r:ao:::¥;¥c:i::
2geg2.
b. If Ao > P (strong field, low spin situation): Pairing will

::vC,unrg£:ot±ei[Link]I,4rg£::[Link]
The pai accur (
remain
iv. Referring to the energy level of an isolated metal atom, the
CFSE = (3 x -0.4 + 0.6) Ao = -0.6 Ao
weighted mean of these two sets of degenerate orbitals is
taken as zero, this is some times called the Barycentre. The dx2_y2,d2

difference in energy between the .two [Link] is given either

of the symbols Ao or 10Ag.
The size of the energy gap Ao between the f2g and eg levels
canbemeasuredeasilybyrecordingtheUV-visiblespectrum
of the complex. Consider a complex like [Ti(H20)6]3+, the dry, dyz. dzx
Ti3+ ion has one d electron. In the complex this will occupy
Fig. 7.33 Weak field
the orbital with the lowest energy, that is one of the f29
orbitals as shown in Table. The complex absorbs light of the CFSE = [4 x (ro.4)] = - 1 .6 AO
 Coordination compounds 7.67

strong field ligands. The comlnon ligands can'be arranged

in increasing order of crystal field splitting Ao. The order
remains practically constant for different metals and this
•;ge: series is called the spectrochemical series, which is as
follows:
|©<Br°<s2-<SCN°<C|®<No3e<F°<urea<8H<
dry. dyz. dzx
C2042-<02-<H20<Scbr9<py,NH3<en<bipy<phen
Fig. 7.34 Strong field
<N02°<CN©<CO
Note: Calculations show that coordination entities with
The series can be split into weak field ligands, border line
four to seven c7-electrons are more le for strong field
and strong field ligands. [refer to section 7.10.2, Point (iv)I
as compared to weak field cases.
The spectrochemical series is an experimentally detemined
c. The CFSE in weak field (Fig. 7.33) is larger than in strong
series based on the absorption of light. It is difficult to
field (Fig. 7.34). However, the energy P used to pair the
electrons must be allowed for, so the total stabilisation explain the order as it incorporates both the effects of
a and 7t bonding. The halides are in the order expected
energy in strong field is -1.6 Ao + P.
from electrostatic effects. In other cases we must consider
d. For a given metal ion P is constant. Thus the amount of CFSE
[Link]
a donation is follows:
i:g::tdeg;:,e8[gy;y:i]e[::]eyngats°efat;::if::I:tt:::d;fAenwe:gi
levels Ao. Thus it will be more favourable energetically for Halide <0 <Ndo
electrons to occupy the upper eg level and have a high spin The crystal field splitting produced by the strong field
complex, rather than to pair electrons. Similarly, strong field
CN° 1igand is about double that for weak field ligands like
ligands (e.g. CN9 cause a large splitting Ao. In this case it
the halide ions. This is attributed to 7t bonding in which the
requires less energy to pair the electrons to form a low spin
metaldonateselectronsfromafilledf2gorbitalintoavacant
complex.
orbital on the ligand. In a similar way, many unsaturated N
Similar arguments apply to high and low spin complexes of donors and C donors may also act as 7t acceptors.
metal ions with d5, cf and d7 configuration as summarised
Ligands given in the borderline criteria act as both strong
in Table.
and weak field ligands. By knowing the value of magnetic
7.11.3 EFFECT OF CRYSTAL FIELD SPLITTING moment, #, it may be suggested that whether they act as
[Link],NH3behaves
::e°rc;ahoefd:al[Link]LpeL:Xtis:ttiea£:LSLnL::foi2egs°trabb£LteaL3yde_Cor.e4asAeos;:: as a strong field ligand and H20 as weak field ligand. The
electrons. compound [Co(OX)3]3-is one of few rare examples where
oxalate ion acts as strong field ligand.
ThFe[:1;:ai:gry°sr:it:[es]in:traeba£S[::attT:ne::re%yb7s+g%#relectron. 2. Charge on the metal ion: The magnitude of Ao increases
CFSE(octchedrai) = [-0.4"(/2g) + 0.6"(eg)] Ao as the charge on the central ion increases.
As the charge on the central atom increases, its interaction
with the ligands increases, thereby leading to an increase
¥gh:rned";:2g:r::tdaL:(erse)s:reec::veeLnyT=::rc°:;:e:::::o°;ocru:oy::8wt]:: in value of Ao.
cP and d]° configurations in both strong and weak ligand fields. It has been observed that for the first row transition metal
The CFSE is also zero for cJ5 configurations in a weak field
(refer to Table 7.18). i::gs;rththeavna:#:Sv::ufso::rM¥:+c:°mmp::::::areroughly50%
3. Size of the metal ion: The value of Ao increases by about
7.11.4 FACTORS AFFECTING THE MAGNITUDE OF
30% between adjacent members down a group of first (3dy),
CF`YSTAL FIELD SPLITTING ENERGY
second (4d), third (5cD series of transition elements in the
The factors affecting the magnitude of crystal field splitting energy order 3d < 4d < 5d.
(Ao) are as follows: As the size of the central atom/ion in the complex increases,
1. Nature of the ligands its interaction with the ligands increases which leads to an
increase in the value of Ao.
2. Charge on the metal ion
3. Size of the metal ion 7.11.5 CFSE AND ELECTRONIC CONFIGURATION IN

1. Nature of the ligands: Ligands which cause only a small OCTAHEDRAL COMPLEX
degree of crystal field splitting are termed weak field Table 7.18 shows CFSE and electronic arrangement in octahedral
ligands. Ligands which cause a large splitting are called complex.
7.68 Inorganic chemistry

Table 7.18 CFSE and electronic arrangement in octahedral d9 1 - 0.4 x 6

I Both WF and SF J53 - \ .J 3
complex + 0.6 x 3--0.6
;:rtf`:rc^,esres:es):3**¥r

E,ec-troni€ -nfigu- - Spinonlv a `neticmomentj](D!=:,`.

se

`se§SgifS,:
flflflLft:28g
`1

\\0 `( -A.r ,'?!'`;,i;:9'Jsy ,L::;:5\--T1,

JS`rfeBM dlo I Both WF and SF 0 - 0.4 x 6 0.00
A:rasQrt r
+ 0.6 x 4--0.00

J` --eg1--t2g I - 0.4 x 1=-0.4

vF3 i 1 .1 3 flflflflfl:2gg

d2 --eg11-t2g 2 - 0.4 x 2--0.8

Ji8i8-2.$3 Note: Symbols use H = octahe
WF=Theconfigura ndw?ckfieldcomplexes,
-0.4 x 3--1.2 SF=Theconfigurationforlowspinandstrongfieldcomplexes,
d3 3
JTE5 - 3 .gJ 7z = Number of unpaired electrons.
1-i-1:28g
-0.4 x 3+0.6x1--0.6
J1
Elil-1;2gg 4
Jir4 -4.9o
Prove that the lowering of the
the raising of the destabilised orbitals is 0.6 Ao

;::`.` The total energy of separation is Ao. Let x = energy

.'`.<.
-0.4 x 4--1.6
Efl-i-i;28g 2 Ji8i8-2.$3 of stabilisation and ); =.energy of destabilisation. Then
)/ -I = Ao. Since the orbitals yield no net increase in energy when
they are equally occupied.
•.. 3jr+2y-0
d5
E1|egilltg 5 - 0.4 x 3+0.6x2--0.0
J535=S.92 3 3x + 2 (Ao + jr) = 0
... 5x=-2Ao j¥=-0.4Ao and)/=+0.6Ao

7.11.6 CFSE OF d-ORBITALS IN TETRAHEDRAL

- 0.4 x 5--2.0 COMPLEXES
Eri-1;28g 1
\F`;`` - 1 I 3
A regularly tetrahedron is related to a cube. One atom is at the
centre of the cube, and four of the eight comers of the cube are
occupied by ligands as shown in Figures 7.35 and 7.36.
- 0.4 x 4+0.6x2--0.4
d6
Hftllll;2gg 4
J5Z -4.9o

- 0.4 x 6--2.4
Efl-ri:28g 0 0.00
(a) (b)
Fig. 7.35 Relation of a tetraliedron to a cLlbe
+z
- 0.4 x 5+0.6x2--0.8
d7
Efllfli;2gg 3
JTi5 - 3 SJ

- 0.4 x 6+0.6x1--I.8
Efllfl-fl:2gg I
Nrs---.\.J3

d8 2 -0.4 x 6
I Both WF and SF Jg -2.83
+ 0.6 x 2--1.2 -Z
fllfllfl:2gg Fig. 7.36 Compete set of d-orbitals in a cubic field. Either set of
tetrahedral(igands(.Oars?Rep::#ccij§eidfieLdone-halfasstrong
 Coordination compounds 7.69

The labels we apply to the two sets of degenerate orbitals

are consistent with their symmetry properties in a tetrahedral
environment: `f2' for dry, dyz and dxz orbitals and `e' for the
dx2_y2 and dz2 orbitals. The `g' subscript which was used for the
octahedral field is no longer appropriate because the tctrahedron
lacks a centre of inversion.
The `/2' orbitals are 0.4 A, above the weighted average energy
of the two groups (the Barycentre) and the `e' orbitals are 0.6 A,
below the average.
The magnitude of the crystal field splitting A, in tetrahedral
complexes is considerably less than in octahedral field. There are
two reasons for this:
1. There are only four ligands instead of six, so the ligand field
is only two thirds the size, hence the ligand field splitting is
d yz dxz
also two thirds the size.
fig. 7.37 0iientation of a orbitals relative to a cube 2. The direction of the orbitals does not coincide with the
The direction jr, )/ and z point to the centres of the faces of the direction of the ligands. This reduces the crystal field
splitting by roughly a further two thirds.
ThusthetetrahedralcrystalfieldsplittingAtisroughly2/3x
;i;:a;ni:z:::[[;t:as::fof:rye::xsi,i:ed::ini,t:e;:l!tf2:-:yo:n:j'e¥;i:Z:t`:b:e:::(e;; 2/3 = 4/9 of the octahedral crystal field splitting Ao. Strong
shorn in Fig. 7.37). fieldligandscauseabiggerenergydifferencebetween`/2'and
`e'[Link],thetetrahedralsplitting
Theligandsdonotdirectlyapproachanyofthemetald-orbitals,
but they come closer to the orbitals directed to the edges of the At is always much smaller than the octahedral splitting Ao.
Cube (dry, dyz and cJxz ) than to those directed to the centres of the Thus it is never energetically favourable to pair electrous,
cube faces (dx2_,2 and dz2). and almost all tetrahedra] complexes are high-spin and
low-spin tetrahedral complexes are rarely observed. One
such example of low spin tetrahedral complexes of first
meTt:Leaa:gL:h:eL¥:::::yh:LffiE;?=tr:a:£¥L°ar:;feL'=th;ogcoe2n8T/a!
- 54044,. row transition metal is tetrakis (I -norbomyl) cobalt (IV).
Rather, under conditions favouring strong crystal fields,
The angle between dx2_y2 and dz2 orbital, the central metal and
the ligand is 35°16'.
other geometries are preferred over tetrahedral structures.
The approach of the ligands raises the energy of both sets of
7.11.7 TOTAL CRYSTAL FIELD STABILISATION
ENERGY
:::]at::[Link]:rgo::rd7o'tdE£:rg[Link]#fs°:#[££:,a;S:pd,,=:nr:
is the opposite way round to that in the octahedral complexes as CFSE(tetrahedrai)=[ro.6#(e)+0.4%(,2)]Afwherero(e)and#(,2)arethe
shorn in Fig. 7.38. nTh:%eFrs°£(eT[:;:s°znesr:Cfcourp£:£nns8w¥:h`e#;'£;0;Po£:;S=e;P::tt££::I,y;
[Link]

both strong and weak ligand field (Refer to Table 7.19).

At
7.11.8 CFSE IN BOTH OCTAHEDRAL AND
- - - Average TETRAHEDRAl. COMPLEXES
enengy level
®arycentre) This shows that for #, d5 and d]° arrangements the CFSE is zero
inbothoctahedralandtetrahedralcomplexes(referTables7.16and
7.17).ForallotherelectronicarrangementsthereissomeCFSEand
[Link] follows
that octahedral complexes are generally more stable and more
common than tetrahedral complexes. This is pally because there
aresixbondenergytermsratherthanfourandpartlybecausethere
is a larger CFSE tern. Despite this some tetrahedral complexes
Fig. 7.38 d-orbjtats s|)Lifting in an tetraltedra( cTystat field are fomed and are stable Tetrahedral complexes are favoured:
Step I: Average energy of the d-ofoitals of metal atom/ion in a 1. Where the ligands are large and bulky and could cause
hypothetical apherical crystal field.
crowding in an octahedral complex.
Step H: Splitting of drofoitals of metal atom/ion in tetrahedlal 2. Where attainment of a regular shape is important. For
crystal field. tetrahedral complexes d), c£, d5, d7 and d]° configurations
are regular. Some tetraledral complexes which are regular
Note:htctrahedralcoxplexes,mostlyA€<P(At=4/9Ao)and
are:
hence they generally fro high spin coxplexes.
7.70 Inorganic chemistry

TiIVC14(e°, t2°), [Mnv]]04]° (e°, t2°), [Fev]04]2-(e°, t2°), i o.6 x 4 + - 0.0 x 4/9
dlo flflfl#:2 0
-0.00
FTeH[C14]©(e2,t23)[CoHC14]2-(e4,t23)and[Zn[]C|4]2-(e4,t26) 0.00 0.4 x 6-0.0
3. When the ligands are weak field, and the loss in CFSE is
thus less important.
7.11.9 CFSE 0F d-ORBITAL IN SQUARE PLANAR
4. Ih7here the central metal has a low oxidation state. This
reduces the magnitude of A. COMPLEXES

5. Where the electronic configuration of the central metal is The square planar geometry may be considered to be derived from
J), d5 or d[° as there is no CFSE. octahedral by removing the two ligands which were approaching
the central atom along the Z-axis (called tetragonal distortion).
6. Where the loss of CFSE is small, e.g. d[ and c¢ where
The splitting may also be explained as the lobes of c7„2_y2 point
the loss in CFSE is 0.27 Ao or # and d7 where the loss is
towards the ligands, this orbital has highest energy.
0.53 Ao.
Though lobes of dry orbital lie between the ligands but they are
7. Many transition metal chlorides, bromides and iodides form
coplanar with them, hence this orbital is next higher in energy.
tetrahedral structures.
The lobes of dz2 orbital point out of the plane of the complex but
the torus around its centre lies in the plane, therefore dz2 orbital is
[Link] Comparison of CFSE and Electronic Arrangement in
Tetrahedral (TH) and Octahedral (OH) Complexes
:::i:£pg,i:re£:fet::rg:inTp|:x],[Link]°eftzxezya:rde?gza:tr:itfi:lest:d°£bn;:hu:
electrostatic field of the ligands, and thus have lowest but equal
Table 7.19 CFSE and electronic arrangement in TH and OH
energy. The average energy of the orbitals remains constant in
complexes
this redistribution of energy as in octahedral and tetrahedral
i - CFSE + +
con- Arrangement qf fl.& TH (CFSE), complexes (the stronger the surrounding field, the higher the
fi8fu e lectrons in .TH "Spin (At) .`y-,``
scaled for com- dx2_}2orbitalwillberaised,howieverthelower,occupiedorbitals
ra«,tioH` conplexe a ParlsooHass(At)=4nw]thuming,19io will drop in energy by a corresponding amount) (Fig. 7.39).
BM

d' ---t2 1 -0.6 x 1 -0.6 x 4/9

1_e --0.6 --0.27Ao
1.73

d2 ---t2 2 -0.6 x 2 -1.2 x 4/9

lie 2.83 --1.2 --0.53Ao

d3 i--t2lie 3
3.87
-0.6 x 2 + -0.8 x 4/9
0.4--0.8 --0.36Ao Removal of z ligands

(a) (b) (c)

-0.6 x 2 + - 0.4 x 4/9

d&
11-t2lie 4
--0.18Ao
Fig. 7.39 d-orbitaLs splitting in a square pLannar field
4.90 0.4 x 2--0.4 (a) An octahedraL complete undergoing z-axis elongation
(b) It becomes tetragonally distorted and
(c) finally reaches the square planar limit
-o.6 x 2 + - 0.0 x 4/9
d5 11|t2lie 5
- 0.00
Note:Thedz2orbitalsmayliebelbwtheeg(dxzanddry)orbitals
5.92 0.4 x 3-0.0 in the square planar complex.

Of 11|t2JLlei 4
4.90
- 0.6 x 3 + - 0.6 x 4/9
0.4 x 3--0.6 - - 0.27Ao ------ I
dx2-y2

+ 0.6Ao
d7 -0.6 x 4 + -1.2 x 4/9
11|t2J[fle 3 I ]t2 dy
3.87 0.4 x 3--I.2 --0.53Ao 11_J1 Ao +0.4A,

ffi£)#:'asl t2:°±¥ ro[6d:orbtfa[;] e dz2

2 -0.6 x 4 + -0.8 x 4/9
d8 I
flllt;JLfle --0.36Ao
2.83 0.4 x 4--0.8 d-orbitals (tetrahedral
(octahedral field) [
field) dxz. dyz
#! JHLlt2JLfle 1 -0.6 x 4 + - 0.4 x 4/9 J-orbitals
1,73 0.4 x 5--0.4 --0.18Ao
`free ions)
-------- " [Link]ield)
planar

Fig. 7.40 Comparison of crystal .,field splitting in all three fields

 Coordination compounds 7.71

The square planar geometry is favoured by metal ions having a d8 configuration in the presence of a strong field. This combination
giveslowspincomplexeswiththeeightd-electronsoccupyingthelowenergydxz,d)z,dz2anddryorbitals,whilethehigh-energyorbitals
remains unoccupied.
7.11.10 COMPARISON BETWEEN THE ENERGY LEVEL DIAGRAM, ELECTRONIC CONFIGURATION AND#spjn
VALUES OF SOME COMPLEXES BY VBT AND CFT

Table 7.20 Based on VBT and CFT, the energy level diagram, electronic configuration of the central metal atom/ion and
HSDin Values Of Some of the complexes
^ ^;\¥£``' ; { ~ `:,:r`\;:i)<,::ir3,;.A;¥;€j.;:`;; ;YY.: :`v??
.No, complexes u v`` r>"f":;,rjt A.<`v`\`;:.^v;Oo?r~ lot.\ ;`'\at\,y Eld€rtronicconfiguration` :rf;:};;=\~~a
v v efectrons
No. Qf{int}
tmpaired
fry CFT #§pin(PIW '
:a diagram
I. INiQVH3)6]2+ Ni(Z = 27) = 3d8 4s2 2
strong field ligandCN-6Octahedral Ji8i8 - 2.$2
Ni2+=(3d8)ion=t6ge3fl¥#o+1I (#L=fl:#eti6g(„=2)(VBT)(CFT)

2. [Cr(CN)6]3- Cr(Z=24)=3d54s' 3
strong field ligandCN-6Octahedral JTE5 -3.8J
Cr3+=(3d3)ion=t23gegi+d+oT_I t±=L:+et:3g(„-3)(VBT)(CFT)

`|#(:tTo,:!4fieid1igand,pairingin`t2g'orbitaloccursCN-6Octahedral
3. Mn(Z = 25) = 3d5 4s2Mn2+=(3d5)ion=t25g eg|1dloil,,#--fl:let:g(„-5)(VBT)(CFT) 1
J53--|.J3

4. [CO(CN)6]3- Co(Z--2:I)=3dn4s2 0 0
strong field ligand,pairingin`t2g'orbitaloccurs
Co3+=(3d6)ion=t26ge;JL|#|I (,f:fl:fet:6g(„-4)IVBT)(CFT)

5. [IrorH3)6]3+ ir(Z--77)=5dn6s2 0 0
strong field ligand, pairing in`/[Link]:Highnuclearchargeonmetaloflowertransition(i.e.,4dor5cDseriesalwaysforms |r3+=(5c¢)ion=t26gegJL+atL[o+1I („fl=fl?#et:6g(„-4)

low spin inner orbital complexirrespectiveofnatureofligand. rvB Tt tcFTt

6. [Fe(CN)6]4- Fe(Z = 26) = 3cf 4s/2 0 0

strong field ligand Fe2+=(3d6)ion=t26ge9JL+atL,o+1I(„fl=fl:#e:g(#-4)(VBT)(CFT)
7.72 Inorganic chemistry

7. [Fe(H20)6]2+ Fe(Z = 26) = 3d6 4$2 4

JZZ = 4.898
weak field ligand Fe2+=(3d6)ion=t24ge:fl+d+[o+1I (#:+:+et:4g(„-4)OuT)(CFT)

8. [Irc16]3- Tr{Z=77)=5dn6st 0 0
In 3rd transition element series,Aoissolargethatitbecomesge:tir.,:h:F©:c:gaaisri;:.: ei:I31igandandthuspairingof`2g' |r3+=(5Of)ion=t26ge8JL1#|, (f--fl:#::g(„-4)

orbital occurs (VBT) (CFT)

9. [ptcl6]2- Pt(Z = 78) = 5# 6rt 0 0

Pt is in 5d transition elementseries,so(P<Ao)Cl©isstrongfieldligandasexplainedaboveinpoint(8) pt4+=(5d6)ion=t26ge8JL+rfL[o+1[(#=fl:#ej:g(„-4)OVBT)(CFT)

10. [Rhqu3)6]3+ Rh(Z = 45) = 4d85$1 0 0

Strong field ligandRhisin2ndtransition elementseries RE3+=(44ion=t26ge9JL+ofL]o+1I(„fl=fl:#ej:g(J,-4)(VBT)(CFT)

11. [Mn(CN)6]3- Mn(Z = 25) = 3d54s2 2

JF8!8--2.82.8
Strong field ligand Mn3+=(3#)ion=t24gegil#-I(Z-12i:!8g¢-4)(VBT)(CFT)

12. [coF6]4- Co(Z = 25) = 3d74s2 2

Jig--2.828
Weak field ligand Co2+=(3d7)ion=t25ge:JL#loili(#:fl:ie:5g(„-3)(VET)(CFT)

:oft:[Link]inghe;::r:;i:fs[t:tr:is23;:]3S[£'nsi::::p°£:[se::e°£:;SxP:£=e8:
Forthecomplex[Crqu20)6]2+,calculatethetctalpairingenergy
/11 eg
in high spin and low spin state. Given the mean pairing energy
= 23500 cm-1.
(d-orbitals)
\llltg
[pnrecs°e:tp[;a;[c:r(h¥:°3)d6j2:;:[££:;:::a+eh:fc::Sgr+i't:;e; Theconfigurationofd4ioninlowspinstateist294eg°,sincepairing
:!=-- ,s
:ofwans::Cstrfa°t::k[esxp;a=eit:t2;;gigs_e]n=r2¥50£[::_i:O)J2+in
 Coordination compounds 7.73

EZ --eg hence high spin state is more stable.

\flllt2g
Give reason for the fact that crystal field theory is rot applied
to complexes of many group metals.
WhichcomplexofthefollowingpairshasthelargervalugofAo. •!`m,I,-i . .
Main group metals do not have incomplete d subshells,
[Link]
or completely field d-subshells, A = 0, hence crystal field theory
;.[ۤg;i;;3]::==d:[i::%3:6)]63]:+ is not applied to complexes of main group metals.
?jji``.i.,.`,

[Link]#Ch¥![Link]t:SrL£:::rs¥aeL:;ift£&ih#3:OorH3)6]",Since
a. Using CFT, depict the electronic configuration of the
ii. NH3 has greater field strength than F© ion, hence Ao will rhodiun ion (Rh2+) in an octahedral field for which the
be greater for [CoOVH3)6]3+. crystalfieldsplittingAoisgreaterthanthepairingenergyP.
b. Calculate the crystal field stabilisation energy for this
iii. Charge on Co in [Co(H20)6]2+ is +2, whereas charge on
configuration (in terms of A and P)

fs°hi:h::t°h(aHn2::6:;=3;:].2:,i::efi::a[r€:a;6:3qsH[3a)r[Link] fiHEife
than [coavH3)6]2+. a. RE (Z = 45) 3 4d8 5s], Rh2+ = 4d7
Rh2+ioninoctahedralfieldhasconfigurationt296eg]when
Cryita;fih:r:±Pitt]n8[A°]Si=i=:re:;hganje:;1;lnpgenergrp

:;I:uo#;r:;hna:n:o:-;;:o:o::os:I-p¥ar:eT::e!,i;I::;;d:;th¥#c:Tp;i-:,x::
have high spin or low spin complexes? Also write the field

configurations corresponding to these states. b. For Rh2+ ion, in octahedral field (Ao > P),
CFSE = |0.4 x 6) Ao + (0.6 x 1) Ao + P
#E::!#h(;¥2£?}6]h3[+g'i°:;fn°:opm(p£:i:]a:%:::;]'o:=1::£:: = -2.4 Ao + 0.6 Ao + P = -1.8 Ao + P
Will not take place). Mn in [Mn(H20)6]3+ is present as Mn3+ ion.
(Even in a spherical field, the complex must have two pairs
Mn3+ionisd4system,itsconfigurationist293eg[.
of electrons, one additional pair is formed in the octahedral
For [Mn(CN)6]3- ion ... Ao > P (Ao = 38500 cm-I, P = field)
28500 cm-I). Hence pairing of electron will take place and the
[Mn(CN)6][Link][Mn(CN)6]3~ispresent
asMn3+ionwhichisd4system,itsconfigurationist294eg°. Whatfactordeterrnineswhetherthecrystalfieldinanoctahedral
complex is to be regarded as strong or weak? How many
d-electrons must be present in orbitals of central atom for
there to be an abrupt change in crystal field stabilisation energy
betveen strong and weak fields?
;:r2!:;(oH£!€:2i]:n;atg±:::opi{on£:g[;;3ro¥[Link]:rcnu€a::
the crystal field stabilisation energy for the complex in REEEHEN Crystal field in an octahedral complex, to be regarded as
configurations corresponding to high spin and low spin states. strong or weak, depends on the relative magnitude of Ao and P.
Which is more stable? a. IfAo>P, Strong field
b. IfAo<P, Weak field
Egur[:tl[ocnrg€?)+6!::i::'dg,rc[2P::;efnntha£Sgfrp:n£::t:s[:e::3°eng£]: Abrupt changes in crystal field stabilisation energy between
CFSE = -3 x 0.4 Ao + I x 0.6 Ao strongandweakfieldsoccurwithd4,d5,c¢andd7configurations.
= -I.2 + 0.6 Ao = -0.6 Ao = -0.6 x 13900 cm-I
= -8340 cm-1 7.11.11 APPLICATloNS 01= CFT
Crystal field theory (CFT) is successful in explaining:
Cr2+ioninlowspinstate:t294eg° i. Stability of the different stereochemical arrangements
CFSE = 4 x 0.4 Ao + P observed in different complexes.
= |1.6 x 13900 + 23500) cm-I ii. Spectral properties of complexes involving d-d transition.
iii. Distortion from the symmetrical geometries with certain
= (-22240 + 23500) cm-I = + 1260 cm-1
limitations.
CFSEforhighspinstateisgreaterthanCFSEforlowspinstate, iv. Magnetic properties of coordination compounds.
7.74 Inorganic chemistry

7.11.12 LIMITATIONS OF CFT planar complexes of Cu(II) are highly distorted octahedral
Crystal field theory is not very clear about the following: complexes.
i. The spectrochemical series: CFT assumes the interaction 3. Tetragonally compressed distorted octahedral complexes.
between central metal atom/ion and ligands in the complex (Also see Fig. 7.41). In an octahedral complex, if the two
to be electrostatic and therefore the anionic ligands should frtz#s ligands are brought nearer to the central metal atom,
the distance of these two trams ligands from the metal atom
The reverse has been
i:y`:*m:_xlLm_I.C_ry.5t_a]f:,I_P±:P]£,i;gE
found to be tine, i.e. halides (X°) are at the bottom of becomes shorter than that of each of the remaining four
equatorial ligands from the central metal atom. Thus the
spectrochemical series (weak field ligands), ©OH, a strong
two trans ligands become shorter than each of the four
basegivesafieldwhichisweakerthanH20(neutralligand
equatorial bonds. The two trams ligands become shorter
and have a larger size).
because these bonds are stronger than the equatorial
ii. The radial wave functions of the d-orbitals a'nd of the ligands bonds. Such octahedral complexes in which the two
should have some overlap at the observed intemuclear trars ligands are shorter than each Of the four equatorial
distances in the metal complexes. The ligands therefore are bonds are called tetragonally compressed (or contracted)
not point charges, but have their own electron orbitals. dz.s/orfedoc/clfeed7ifl/co"p/[Link]
iii. The CFT carmot account for the 7t-bonding in the complexes. tetragonally compressed distorted octahedral complex is
iv. CFT cannot explain the charge transfer spectra and the ca,lied tetragonal contraction distortion.
intensities of the absoaption bands. These are some of the
limitations of CFT, which are explained by ligand field
theory (LFT).

AHN-TELLER EFFECT AND

DISTORTION IN OCTAHEDRAL
L
AN D TETRAHEDRAL COMPLEXES Regular octahedral complex, M(Le)4 (Lo)2
(M - La=M-Lc or a = e)
Distorted Octahedral Complexes
Tetragonal Both La
In an octahedral complex all the six M - L (L = ligand and M = elongation ligands
central metal atom) bond lengths are equivalent. If M - L bonds (z-axis out) removed
are of unequal lengths, the octahedral geometry of the complex
gets distorted and we get distorted octahedral complex.

7.12.1 TYPES OF DISTORTED OCTAHEDRAL

L,,`-i
COMPLEXES
I. Tetragonally elongated distorted octahedral complexes: -ts,,'L Jf i-,:-` Le
(AlsoseeFig.7.41).Thesecomplexesarealsocalledsimply
[Link]
anoctahedralcomplex,ifthetwotransoraxialligands(La) Tetragonal elongated Square planar Tetragonally compressed
distorted octahedral complex complex distorted octahedral complex
are moved away from the central metal atom, the distances of
(M - La > M - Lc or a > e) (M - La < M - Le or a < e)
these two ligands from the metal atom becomes larger than
thatofeachoftheremainingfourcoplanarequatorialligands fig. 7.41 Different types of distorted octahedral complexes

(Lo) from the central metal atom. Thus the two trans bonds 4. Trigonally distorted octahedral complexes: Trigonal
(alsocalledaxialbonds)ormetal-ligandbondsalong+zand prismatic complexes: When an axis passing through the
-zaxesbecomelongerthaneachofthefourequatorialbonds
centres of the two opposite triangular faces of an octahedron
(equatorial) bonds are metal-ligand bonds along +x, -x, +)/ is increased (elongation) or decreased (compression or
and -); axes in xp; plane. The fr¢#s bonds become longer contraction) in length, octahedral complex gets distorted
because these bonds are weaker than the equatorial bonds.
and assumes trigonal prismatic geometry (See Fig. 7.42).
[Link] octahedral complexes in which the two trans ligands
I
are longer than each Of thef;our equatorial bonds are called La
tetragonal|y elongated distorted octahedral complexes
or simply tetragonally distorted octahedral complexes Let,`-,:,-?-`:;jLe
Trigonal Trigonal
M` contraction
(See Fig. 7.41). The distortion which gives tetragonally
Lei(-,--i--;iLe
distortedoctahedralcomplexiscalled/eJrtzgo#¢/e/o#grfz.o#
distortion. La
2. Square planar complexes: (Also see Fig. 7.41). Some times t
Tdis8t:nrtae]:y Regular Tdi8t:nri:iy
thetetragonalelongationdistortionintetragonallyelongated octahedron
octahedral complexes is so large that the two trams ligands . octahedron (DOA) octahedron
(D3d) (D3d)
on z-axis are completely removed and hence octahedral
[Link] Fig. 7.42 [Link] distortion in an octahedral ML6 complex
 Coordination compounds 7.75

7.12.2 TYPES OF DISTORTION IN OCTAHEDRAL in such a way that the symmetry and energy of the molecule /
complex is lowered and hence the molecule / complex becomes
COMPLEXES
more stable. This theorem does not say which type of distortion
The forgoing discussion clearly shows that the octahedral
will occur in the molecule / complex. Thus, according to this
complexes can undergo the following types of distortion.
theorem, if the electrons in d-orbitals of the central metal ion
(i) refrczgo"cz/ [Link].o#. This distortion is of the following two of a regular octahedral complex are asymmetrically arranged,
types: the octahedral shape of the complex will get distorted, since the
(a) Tetragonal elongation distortion electrons present in a symmetrically-filled d-orbitals will repell
(b) Tetragonal contraction (or compression) distortion. some ligands to greater extent while other ligands will be repelled
to lesser extent. The distortion in geometry of non-linear system
(ii) Trigonal distortion
due to Jahn-Teller effect is called Jahn-Teller distortion.
(iii) Rhombic distortion.
7.12.3 DISTORTION SHOWN BY 0CTAHEDRAL
[Link] Symmetrically and Asymmetrically
cOMPLEXEs OF dr ioNs (x = o TO io)
(Unsymmetrically) Filled t2g and eg Sets of
Octahedral complexes of some dx ions show strong distortion
Orbitals
while some ions show weak distortion. There are also some ions
[ff2gsetoforbitals( e.,dry,d}zandd2*orbitals)contains0(empty,
which do not show any distortion.
f8g): 3 (half-filled, f
g) or `6 (`completely-filled, J8g) electrons, the
arrangement (distribution) of these electrons in this set is said 1. „ ion (f2g c! with « = 0): Octahedral complexes of at ion
to be symmetrical arrangement and f2g set of orbitals is said to do not show any distortion. Examples of such complexes
are [Tix6]2-where X = F, Cl.
be symmetrically-filled. On the other hand, if /2g set contain 1,
2, 4 or 5 electrons, the arrangement of these electrons is said to 2. dL ion. Tis+ ion is a d) ion: This ion is present in
octahedral complex ion, [Ti(H20)6]3+. In the ground state
asymmetrical arrangement and J2g set of orbitals is said to be
asymmetrically filled. Thus : d] configuration is represented as /2g e8 ,Z!g electron may

(i) f2g (empty), f32g (half-filled), f€g (completely-filled)...

symmetrically filled orbitals. :sepprreesseenntt]]nndd;oorrbb]:taa[:i¥i(f:zoo)::!f;;nwunhune:er':3e:I:::::
distortion and assumes compressed distorted octahedral
(ii) /ig. f?2g, f2g, f2g ,... asymmetrically-filled orbitals.

g:zoo:e;:.o:b:t:T,e[:::fir2g;:]d3'+I:n';:rg[Link]Pdr£::::t£;:
::)e,82Se(th°[Link]i::ad)Sc(:);e;'rdz2(-c#et%L2y°:i::adL,S)e:)ase:eecrt°ro(::Ptg: and assumes elongated distorted octahedral geometry.
arrangement of these electrons in this set is said to be symmetrical
3. d2 ion: E.C. of d2 ion is /2g e8 (# = 2). This configuration
arrangementandegsetoforbitalsissaidtobesymmetricallyfilled.
On the other hand, if eg set has I or 3 electrons, this arrangement
Eaesn::yo¥::icaa,1:yo£[::edx`e2§o0fb#;::::;:I?gtyhteg£:trob#ao`::
of electrons is said to be asymmetrical arrangement of electrons
and eg set is said to be a symmetrically filled. Thus: 4. # ion: E.C. of d3 ion is f2g e8 (# = 3). In this configuration

(i) eg (empty), e: (half-filled), e: (completely filled) ...

3%:ar£::I:L[Link]#::|Cfa;]3y]giL,etdh:edfi::e:r:;t:1;t¥:oe::nty;
symmetrically filled orbitals
distortion (no distortion). Examples of such complexes are
(ii) e:, e: ... asymmetrically-filled orbitals. [Cr(or)3]2-, [Cr(H20)6]+3 etc.
5. (a) d`(HS) ion: Cr2+ and Mn3+ ions are c¢ ions. Since the
Note: We know that cZ3 ion is represented by the configuration,
configuration of weak field (HS) 6-coordinated complexes
J8g, €: in LS octahedral complexes. In this configuration, both
theelectrousofegsetareassumedtobepreseutincJz2orbitaland
d£ _ y2 orbital remains vacant. This £€g e: configuration is :hfets:e:::°p::x:[szsi2o8we;tr:::::#::£Cna:[hye-I:I:ecdfai%ie:i
shape. One electron present in eg set may be present either
representedasf€g&z2#2_,[Link],althougheg
set is half-filled, it is said to asymmetrically filled, since both
the eleetrons are in dz2 orbital.
:;:;§2:I:°:r:b:;;:f:or:Lr::]e:s:i:sziy;i:1:oai2;;:tbi;[Link]t#y::a:n:d:;;
[Link] Jahn-Teller Theorem or Jahn-Teller Effect axes. On the other hand, if the single electron is assumed
• to be present in orbital, this electron is repelled by two
ln 1937, Jahn and Teller put forward a remarkable theorem
ligandslyingon+zand-zaxes.Thustheenergyofdx2_},2
to explain why some six coordinated complexes (octahedral
complexes) undergo distortion and have distorted octahedral orbital increases relative to c7z2 orbital. This leaves c7x2 _ ,,2

geometry. This theorem states that if a molecule / complex orbital empty. Thus the configuration of # ion in high spin
possessing any shape (excepting linear shape) has an octahedral complexes is (/2g)3(C7z2)I(dx2_,,2)°andnot
unsymmetricany filled set of degenerate orbitals is unstable
and hence undergoes distortion. This distortion takes place (t2g)3(dz2T°(dx2_y2)i .Therepulsi6nbetweenthesingle
7.76 Inorganic chemistry

electron present in c7z2 orbital and the two ligands along +z octahedral complexes of cf ion, therefore, undergo slight
distortion. Example of such complex is [CoF6]3-.
and -z axes (trans or axial ligands) results in the elongation
of the two axial ligands. Thus the octahedral complex (b) d6qs) ion (e.g. Co3+ ion): E.C. of c¢ ion in LS states is
assumes elongated distorted octahedral structure in which /£g eg (# = 0). This configuration has symmetrically filled
twotransmetal-ligandbondsarelongandfourmetal-ligand
bonds in xp; square plane are short. In the formation of :2ogm°;]be£::[sSo:natd]:::;ydeer8go°:bo]tda£[sst.o:i:::eEXLasm:::aohfes:rca£
elongated distorted octahedral structure both f2g and eg sets octahedral complex is [Co(N113)6]3+.
present in octahedral complex split. The splitting of f2g and
8. (a) d7(Its) ion: E.C. of d7 ion in HS state is /£g e3 (# = 3).
Thisconfigurationhasasymmetricallyfilledf2gorbitalsand

:¥#i::Ct£[e[refo[:::s:8o:r:i::[hs;d¥ssto°:::::dralcomplexes
;ie§;eios:wi:Fr¥;:i§rd;°{:ill:¥=¥r:::r;::;i:d:;dte:h;::#,Shd§::jia:
is very small and hence each of these orbitals also has one a) d7qs) ion (e.g. Co2|: E.C. of d7 ion is LS octahedral
electron only. Example of elongated distorted octahedral complexes of this ion is. ffg e: (# = 1). This configuration
complexes containing c¢ ion are CaF2 and MnF3 crystals has symmetrically filled f2g orbitals and asymmetrically
and [Mn(H20)6]3+ and [Mg(C204)3]3- ion. CrF2 Crystal filled eg orbitals, e: electrons is present in dx2 orbital and
has distorted rutile (Ti02) structure in which Cr2+ ion is C7x2 _},2 orbital is vacant. Thus ffg e: = ffgd:2 d±2_y2
octahedrally surounded by six F- ions (ligands). The length d£2_,,[Link]-filledeg
of four Cr+2 - F bonds in ry plane is [Link] each and that
of the two Cr2+ -F bonds along z-axis is 2.43A. Thus the orbitals in ffge: configuration, LS octahedral complexes of
crystal of crF2 has elongated distorted octahedral structure. c77ionundergolargedistortion.[Co(diars)3]2+isanexample
of octahedral complex which undergoes large distortion.
Fig. 7.43 shows that the distribution of cr electrons in the
9. (a) d8 ion (HS) (e.g. Ni2+): E.C. of d8 ion in HS state is
splitted d-orbitals is as cJJz c7; c/; d!2 d£2 _,,2 .
ffge2 = /£g d!2 di2 _,,2 (# = 2). In this configuration f2g
and eg orbitals both are symmetrically filled. Hence HS
(asyrmetrically- octahedral complexes of d8 ion do not show any distortion.
-----i-i
H if H H
z2 Examples of such complexes are INiF6]4-, [Ni(H20)6]2+,
(a) Five degenerate :
d-orbitals of d4 ion i
_i [Ni(N113)6]2+ etc. Energy level diagram showing the filling
lil____i .t-t. of 3c7 orbitals with d8 electrons is given in Fig. 7.44.
`2g i``,_i i)f23g£S[¥e¥ethcauy-
; : J'ZZX
+e+(((::i:dd2£-'}e3f:I:#ethcally-
#)ats::i:¥ng;t°sfodc-t°ibe;i::§i (ocf)gil:#?ng£:sfed[:nr:;tta±S
; complex i distorted octahedral complex

t'
fig. 7.43 [Link] of d4 eLectrons in [Link] and tetragonaLLy
elongated distorted octahedraL complexes of d4 ion. Jitl-4/// dry f26gi;t#Tetrically-
'2g `,\`_lil
(b) d4(LS) ion: E.C. of cr ion in LS state is /£g e8 which
dyz dzx

::?{tt:£L::Lass¥=eet£::]c]:mfi:::£e:2gf°;b;i::1,Sthae::fi:r:?s¥oewg Fig. 7.44 Energy Level diagram showing the [Link] of 3d orhitaLs with
slight distortion. eight eLectrons of d8 configuration in HS sate

6. (a) ds(HS} ion (e.g. Mn2+, Fez+ etc.): E.C. of d5 ion is (b), d8 (LS) ion (e.g., Ni2+, Pd2+, Pt2+ etc.): E.C. of d8
HS state is /2g e: (# = 5). This configuration shows that ion in LS state is /£g e3 = fgg d22 d:2 _ ,,2 (# = 0). In this
configuration,/[Link]
fi8saoncdtaige:bLftca:Sin::::e:r:fs%g=:t::ail:tfiuL:::ig:e::; eg orbitals are half filled, these orbitals are said to be
distortion. Examples of such complexes are [MnF6]4-, asymmetricallyfilled,sinceboththeegelectronsarepresent
[FeF6]3-etc.

(b) d5ajs) ion: E.C. of d5 ion in LS state is /£g e8 (# = 1). ;:o%2[ar°gr:££:sio::::egr::n:Cet]¥neg¥e[dc:i?t:Lrie::So:tfa£:d£:a:

Thisconfigurationhasasymmetricallyfilledf2gorbitalsand [Link][Mg(diars)212]°
where M = Ni2+, pd2+, pt2+.
¥e?g:8s:::itta:S£.sFoerfn£::TS°Ctahedralcomplexesofd5ion The splitting of f2g (lower energy) and eg (higher energy)
7. (a) d6urs) ion (e.g. Co2+ ion): E.C. of d6 ion in HS state orbitals in elongated distorted octahedral complexes takes
is /£g e3 (# = 4). This configuration has asymmetrically place as shown in Fig. 7.45. This figure shows that the
distribution of d8 electrous in the splitted d-orbitals is as
filled C2g orbitals and symmetrically filled eg orbitals. HS
d2yzd2nd2xyd22d°x2_y2.
 Coordination compounds 7.77

Since all electrons are present in the paired state, these and assume either elongated distorted octahedral geometry
complexes are diamagnetic. The elongation of axial bond or compressed distorted octahedral geometry. If /£g e:
lengthsinINi2+(diars)212]°isSolargerthatINi2+(diars)212]°
assumes square planar geometry.
::snufii8eusr:::°n:aLt:d`5d:s?[Link]o-c¥=e:CatL[Link]ia:£:°omne::
t' e3f#gFTetrically other hand, if ffg e3 configuration is /£g d!2 d?2 _,,2 ,
eg
the octahedral geometry assumes compressed distorted
NTs=::n_g,:,_n_e__+:df;,:2
----------------+----
octahedral geometry.
|E
i:).rFbily:,S::eE::# The splitting of f2g and eg orbitals in elongated distorted
metal ion
..T i-~ ) f269 1;,getncally- octahedral and compressed distorted octahedral geometry
i dyz dzx has been discussed on the subsequent pages of this chapter.
i (b) Splitting of d-orbitals
' ofd3(LS)Ion :
(c) Splitting ofd-orbitals
I in octahedral complex i in elongated (elongation along z-axis)
distorte:fo#Les#::°mpLex
LL.::L#:r:t::c;[Link]%nh:e:[Link]=gp:;::t:a°LoS;#g:;Sny,;:in::ottr]s:ha:I;

fig. 7.45 Splitting of d-orbitals in tetragonally elongated octahedral distortion. Examples of such complexes are [Zn(NH3)6]2+,
complexes of d8 in LS state [Zn(H20)6]2+ etc.

10. d9 ion (e.g. Cu2+ ion): E.C. of d9 ion (Cu2+ ion) is /gg e: Whatever has been said above has been summarized in
Table 7.21. The information given in this table can be used to find
(# = 1 ). In this configuration f2g orbitals are symmetrically
out the conditions under which the octahedral complex of a given
:i[::o::::r°et:e:8e°:%:[=ee:?c¥:tirifecdale[:o:;]i::|s]tth;: dr ion (x = 0 to 10) undergoes no distortion, s/[Link]/ disforJ!.o# or
octahedral complexes of Cu2+ ion undergo large distortion \allge distortion.

Table 7.21 Summary of distortion taking place in octahedral complexes of dx ions (x = 0 to 10), sym. = symmetrically
filled, asym. = asymmetrically filled.

d* ion•,,,(.A=oto 10) Natureoft2gand€g%^;=S~;`::Iarbita,s

ffg e8 configuration '%gfffsegrasaeg§~S<FSfg;:::r/

tzg i eg

J) Empty i Empty No distortion

•2ge8

d` Asym Empty Strong distortion (Compressed distortion)

•ige8-d;did%e8

Asym Empty Large distortion (Elongated distortion)

/2g e8 = d& di cJ& e8 or d& d% di e8
I Empty
J2 Asym Slight distortion
•2geg

d3 Asym Empty No distortion

2g eg

d4 (HS) Asym Asym Strong distortion (Elongated distortion)

/3ge:=f2gd;2d£2_y2

# (LS) Asym Asym Slight distortion

fgeg

d5 qs) Sym Sym No distortion

2g e3

d5 (LS) Asym S light distortion

•fgeg
i Empty
d6 (HS) Asym Sym S light distortion
fge3 .

d6 (LS) Sym Empty No distortion

!ge8

d7 (HS) Asym Sym Slight distortion

•;ge:
7.78 Inorganic chemistry

d7 (LS) Sym AsymI Large distortion

ffge:=fggd:2d£2_y2

d8 (HS) Sym SymI No distortion

t8g e2g .

d8 (LS) Sym Asym Large distortion (Elongated d`istortion)

t8ge2g=tggd22d°x2_y2

d9 Sym Asym Large distortion (elongated distortion)

tfge%=t8gd22d\x2_y2

d9 Sym Asym Large distcution (elongated distortion)

tfge3g=tzgd\z2d2x2_y2

dl0 Sym Sym No distortion

2g e!

[Link] Conditions for No Distortion

octahedralcomplexesofd8ion(c78=/£ge3=ffgd22c7£2_,,2)]
Octahedral complexes of cF ions whose both the sets of d-orbitals
undergo strong distortion and assume either tetragonally elongated
distorted octahedral geometry or compressed distorted octahedral
Lird£;fgaonfoea:srteosrt¥£::,Csaj:yh:I:emdp{:2x8e's`:r8e'::8rf::t:ye:;t:i'eeja)1 geometry.
in shape. Perfectly octahedral shape is because of the fact that Thus the octahedral complexes of the following # ions undergo
the electrons present in symmetrically filled f2g and eg sets repell strong (large) distortion.
all the six ligands to the same extent. This discussion shows

that since the ions viz d°(/2ge8,#=0), c73(/2ge8,#=3),

d](/!ge8),d4(HS)(/2gd!2d£2_y2-elongateddistortion),

d5(/2g e3 -HSwith % = 5), c76(/£g eg -LS with # = 0), d7(LS)(ffge:.=/£g[Link]_y2)9

d6(/£geg -LSwith#=0), and d8(ffge3 -HSwith#=2)

d8(LS)(ffge3=/ggd22d?2_y2-elongateddistortion),

d[°(ffg eg with # = 0) have f2g and eg sets symmetrically filled,

d9(/gge3=/£gdz22d;2_y2-elongatedqistoltion),
octahedral complexes of these ions do not undergo distortion, i.e. ,
these complexes are perfectly octahedral.
d9(ffge:=/£gd!2d:2_y2-compresseddistoftion).

[Link] Conditions for Slight (Negligible) Distortion Cause of large (strong) distortion: Since the lobes of both
Octahedral complexes of d* ions whose f2g set of orbitals orbitals of eg Set (c7z2 and dz2 _,,2 orbitals) lie directly in the

is asymmetrically-filled (fig,/2g,/£g,ffg) and eg sets is path of the six ligands (six ligands of an octahedral complex lie
on the three axes), the electrons present in this set, if arranged
symmetrically-filled (eg , e3 ) undergo slight distortion. Small
asymmetrically)i.e.,ifegsetcontains1or3electrons),repellsome
distortion is because of the fact that since the lobes the three ligands to greater extent and repel other ligands to lesser extent.
asymmetrically-filled orbitals of f2g set do not lie directly in the This ligand repulsion causes large distortion in octahedral shape
pathoftheligands,theelectronspresentin/2gsetoforbitalscause of 6-coordinated complexes.
small distortion in octahedral complexes. Thus the octahedral
[Link] Splitting of t2g and eg Orbitals in Elongated
complexes d2(/2ge3,#=o), d4(/£ge8 -LSwith#=2),
Distorted Octahedral Complexes of Cu2+ Ion
d5(/£ge8 -LSwith#=1), c75(ffge3 -HSwith#=4), and
The splitting of f2g and eg sets of orbitals into various d-orbitals
d7 (ffg e3 - HS with # = 3) ions undergo small distortion. has been shown in Fig. 7.46
In order to explain the splitting pattern shown in Fig. 7.46, we
[Link] Conditions for Large Distortion
start with the splitting of d-orbitals in f2g and eg sets in octahedral
Octahedral complexes of d¥ ions whose f2g set is symmetrically- complexes. We know that in the splitting ofd-orbitals in octahedral
complexes, the energy of Z2g set (i.e. c7ry, d,z and dar orbitals) is
filled (fgg, /2g and/£g) and eg set is asymmetrically-filled

:neccrreeaasseed:#wt::te::neg[Link][Link].;£:2daoncdtadhx:d-r%i::bitpa::ie::
[e:(d:2 d:2_y2). e3(dz22 d;2_y2)] c3(d:2_,2 d:2) [e3 Set
since metal-ligand bond distance along z-axis is longer, c7-orbitals
having z component (i.e., cJyz, c7zx and dz2 orbitals) experience
(d£2d:2_y2)isalsoregardedasasymmetrically-filledsetinLS
less repulsion from the ligands than they do in octahedral complex
 Coordination compounds 7.79

:xhp£::,:::ed;°::eft::;:fs£?n::::eth(e£;e.;od?naoncdtadhx:d-rz:c°ori£;:lest ##ifi#xF-y2
Consequently the energy of c7yz , c7zx and c7z2 orbitals decreases -,£g+c?g-
whilethatdryandc7x2_,,[Link] Energy increasing >

orbitals still remairi degenerate as they are in octahedral complex.

[Cu(H20)6]2+ ion also has tetragonally elongated distorted
Above [Link] shows that the order of energy of the splitted- octahedral geometry. The tetragonally elongated geometry
orbitals in tetragonally elongated octahedral complex becomes as:
(distorted octahedral geometry) of [Cu(NH3)4(H20)2]2+ and
(dyz = dzx) < dry < dz2 < dx2 _ y2 (Also see Fig. 7.46) [Cu(H20)6]2+ ions is due to the asymmetric arrangement of three
The relative order of energy of various orbitals shown above electrons in eg orbitals. This arrangement contains two electrons
indicates that in the elongated distorted octahedral complexes the in C7z2 orbital and one electron in dx2 _,,2 0rbitals, Since dz2

distribution of 3# electrons (/£g e3) of Cu2+ ion is as shown in orbital has lower energy than c7x2 _y2 orbital. The effect of the
Fig. 7.46. This figure shows that the arrangement of d9 electrons asymmetric arrangement of three electrons in eg orbita]s on the
in various d-orbitals can be written as: octahedral geometry of the complex ions is called Jahn-Teller
d2yz,d2x,d2ry effect.

e3 7.13 TRANS EFFECT

Trans effect is the labialization (making more reactive) of ligands
that are trams to certain other ligands, which can thus be regarded
tte3 ,
No splitting line 'dl_\2d? e3ffli:dTethcally- as trams, directing ligands. It is attributed to electronic effects and
it is most notable in square planar complexes, although it can also
t' t' tl t' t ---Ao===61>82 be observed for octahedral complexes. The cis effect is most often
(a) Five degenerate observed in octahedral transition metal complexes.
d-orbitals in free Cu2+ ion
In addition to this kinetic trams effect, trams ligands also
JLJLJL_ 26gffl::dTethcally- have an influence on the ground state of the molecule, the most
dry dye den
notable ones being bond length and stability the tern trams
26g influence is sometimes used to distinguish it from kinetic effect
however more specific terms such as structural trams effect or
(b) Distribution of 9 (c) Distribution of 9 electrons
thermodynamic trams effect is also used.
electrons in d-orbitals in d-orbitals of cu2+ ion in its The intensity of the trams effect (as measured by the increases
of cu2+ ion in its elongated tetragonally distorted
in rate of substitution of trans ligand) follow this sequence.
octahedral complex octahedral complex

C2H4, CH©, CO,NO, H° > CH9, SR2, ASR3,

Fig.7#ittDejgt#:E.i::I:fin9aihe±:t:¥,::n3S#aLL:i;;::#a(tceud2+dj=st3odrt9!djnthe
PR3 > SO;2 > C6H9, SC(NH2 )2 , NO9, SCN°

> |0 > Br° > C|° > py > NH3 > OHO , H20, F°
Thus the configuration, /gg e: can be written as:
©
(i) (CN°, CO and NO are powerful trans directions while OH
t8ge3g--tfgd22d:x2_y2 •and H20 are very poor.)

This configuration shows that tetragonally elongated octahedral (ii) M-X bond is more labile than M-N bond.
complexes have two electrons in cJz2 orbital and one electron in Example: The classical example of the trams effect is the synthesis
dx2_y2orbital,Sincedz2ortbialhaslowerener8ythandx2_},2 of cisplatine and its trams isomer. Starting from [Ptc14]2-, the
first NH3 ligand is added to any of the four equivalent position at
orbital.
random. However since C1° has a greater .trans effect than NH3,
[Link] Elongated Distortion in Octahedral Geometry of the second NH3 is added trans to a C1° and therefore cis to the
first NH3.
[Cu(NH3)4(H20)2]2+ and [Cu(H20)6]2+ Complexes
Tetrammine copper (11) complex, [Cu(NH3)4]2+ is actually
[CuOVH3)4(H20)2]2+ in which the two axial H20 ligands are
at larger distances (along the z-axis) from the central Cu2+
ion the four equational NH3 ligands are of shorter distances
(along x- and )/-axes). Thus this complex has two long (axial)
ccjE3:+ccjEstFTH3
and four short (equational) bonds. Consequently the complex,
[Cu(NH3)4(H20)2]+hastetragonallyelongateddistortedoctahedral
geometry.
The distribution ofJ9 electrons of cu2+ ion in five d-orbitals is as:
7.80 Inorganic chemistry

If, on the other hand, one starts from [PtovH3)4]2+, the trans Limitation
product is obtained instead: (i) Ammonia which cannot form 7t-bonds should not be
destabilized by the 7t-bonding ligands.
(ii) 7t-bonding alkenes show trams effect for halogens but not
for the nitrogen ligands.

HH3:grET+H:NEECH: (iii) Many ligands like hydride (H°) or methyl are good trams
directors but cannot form 7t-bond.

+ NH3
H,N
CIN H3

The correct increasing order of trams-effect of the following

species is:

a. CN© > Br© > C6H5© > NH3

Hxplanation: The trams effect in square planar complexes can be
explainedintermsofanaddition/eliminationmechanismthatgoes b. NI3 > CN° > Br© > C6H5©
through a trigonal bypyramidal intermediate ligands with a high
c. CN© > C6H5© > Br© > NH3
trams effect are in general those with high 7t-acidity (as in case of ©
d. Bra > CN© > NH3 > C6H5
::#:;i%;}:rh];:¥-pLi::enrdti°eni:::r#[Link]S:::osr{:::ft:sa::
the intermediate. The second equatorial position is occupied by the rare c. The intensity of trams effect-depends on increase in
i;Tt-6 6f substitution of the trans ligands CN° > CH3© > C6H5° >
incoming ligand, due to the principle of microscopic reversibility,
Br° > C|° > NH3 > F°.
the departing ligand must also leave from an equatorial position.
The third and final equatorial site is occupied by the trams ligand,
so the net result is that the kinetically favoured product is the one
in which the ligand trams to the one with the largest trams effect Jahn-Teller effect is not observed in high spin complexes of
is eliminated. g|. di b. dfl
Structural trams effect: The structural trams effect can be c. di a. rf
measured experimentally using x-ray crystallography, and is
c. Jahn Teller effect: This is geometric distortion which
observed as a stretching of the bonds between the ligand and the ;` .`..

occurs in unsymmetrical octahedral complexes.

ligand trams to a trams-influencing ligand.
Stretching by as much as 0.2A occurs with strong trans- For example: High spin complexes of (high spin)
influencing ligands such as hydride (H°) ion. A cis influence
can also be observed, but is smaller than the trams influence. The
relative importance of cis and trans influences depends on the
formal electronic configuration of metal center, and explanations
d4 c7
have been proposed based on the involvement of the atomic Unsymmetrical Unsymmetrical
orbitals.
Factors: The trams effect is used to distinguish between the cis
and the trams isomers of the type [Pt A2X2] where A = amine and
X = halide.
(i) Thiourea (tu) replaces the halides only in the trans isomer d8 cP
but all the four ligands are replaced in the cis-isomer. Unsymmetrical Unsymmetrical

(ii) Trans effect is important with the large polarizable metal Jahn Teller effect is not observed in d8 configuration.
ions, the order of metals is: Pt+2 > pd+2 > Ni+2.

(iii) The trams directors are either polarizable (1°) or multiple

bonded (CO, CN° etc.).
Explain the following giving reasons:
(iv) The two 7t-ligands, for the d-orbitals of the metal ion, will
tend to labilize each other when present trans to each other, a. [Nic14]2- is tetrahedral and paramagnetic, whereas
but in the cis-position they will not complete. INi(CN)4]2-issquareplanaranddimagnetic.
(v) The stronger 7t-bonding ligand will dominate and weaken b. Ire(H20)6]3+ ion is more paramagnedc than pee(CN)6]3-ion.
the other bond. c. ivi(CO)4 is tetrahedral while INi(CN)4]2-ion is square planar.
(vi) In [Pt C13(C2H4)]°, the Pt-Cl bond traps to (C2H4)
d. [Coq6)]3~ is a high spin complex where&s [Co(CN)6]3~ ion
(ethylene) is larger than the cis-bond.
is a low spin complex.
(vii) Pt-Cl (trams) stretching frequency is lower than the
P|1 (cis) frequencies showing weaker PLJl bonds trans
to ethylene group.
. . !`.`?

a. In the complex, [Nic14]2- and INi(CN)4]2- oxidation state

of Ni is +2
Electronic
configuration
ofFe3+in
|m
Coordination compounds

d2sp3
7.81

4s4p
Electronic
configuration
3d8 4s2
3d
mm [Fe(CN)6]3-ion

i.e. there is only one unpaired electron, # = 1.

|m
of Ni atom Since in [Fe(H20)6]3+ ion, number of unpaired electrons

Electronic 3d8 4s°

:::a::::ett:ca:h:=e{Fce}%6rd;:];?:;n[Fe(H20)6]3+ismore
C. In Ni(CO)4, oxidation state of Ni is zero.
::#igT::tion
3d ds 4p
SinceC1°ionisweakfieldligand,electronicconfiguration
of Ni2+ in INic14]2-remains the same,
Electronic
configuration
mm
of Ni atom (3d8 4s2)
ds4p
Ni2+ ion
in INic14]2-) Fmt sp3
Since CO is strong field ligands, hence pairing of electrons
takes place.
3c' 4p
Since Ni2+ in [Nic14]2- ion is sp3 hybridised and have two
unpaired electrons it is tetrahedral and paramagnetic.
Ni atom in
INi(CO)4] ff-A Sp3
SinceCN©ionisstrongfieldligand,electronicconfiguration
of Ni2+ in lNi(CN)4]2-is Because of sp3 hybridisation, [Ni(CO)4] is tetrahedral.

Ni2+
in INi(CN)4]2-
3c'

tt lm 4s4p In [Ni(CN)4]2-, oxidation state of Ni is +2

Ni atom
3d 4s
mm
4p

ion dsp2 hybdridisation

i.e., one electron from 3dx2_y2 orbital gets paired with that
in 3dz2 orbital. Thus one d-orbital (3dx2_)2 orbital) becomes
Ni2+ a,om
lm
Since CN° is strong field which results in pairing up of

available for dsp2 hybridisation which gives square planar :|eaciTa°bTepfroers;:;2±iy3b`rxL2d-]ys2at:::.3dz2and3dx2_rfbecomes

Em
geometry with # = 0. Thus INi(CN)4]2-is diamagnetic. ds4p
b. Oxidation state of Fe in [Fe(H20)6]3+ion is +3. Ni2+
(in INi(CN)4]2- [111
3d 4s 4p 4d ion)
Electronic
configuration
mm dsp2 hybdridisation

ofFe(3d64s2) d. [CoF6]3- is a high spin complex whereas [Co(CN)6]3- is a

low spin complex. This can be explained as:
Electronic 3d 4s 4p 4d
configuration
of Fe3+ ion (3d5 4s°)
Co atom
(3dn 4s2)
mum
SinceH20isweakfieldligand,nopairingofelectronstakes
place and
co3+ ion
(3dn 4sO)
(„ - 4)
lm
Electronic
configuration
Iud
+A
(free state)

co3+ ion
Iud
of Fe3+ in sp3# (in [CoF6]3~) 4t
[Fe(H20)6]3+ ion sp3 d2 hybridi sation
SinceF®ionisweakfieldligand,nopairingupofelectrons
i.e. there are 5 unpaired electrons, 71 = 5.
present in 3d orbital takes place. Since there are four
Whereas in [Fe(CN)6]3-, oxidation state of Fe is +3. unpairedelectrons,[CoF6][Link]

Electronic
3d
fi ffi outer d orbitals (i.e. 4d) are involved, it is also known as
high spin or outer orbital complex.
::##a(t#4:i, Note: Oxalate generally behaves as a weak field ligand
SinceCN©ionisstrongfieldligand,pairingupofelectrons but with Co, it behaves as a strong field ligand like NH3
in 3d orbitals takes place i.e. and H20.
In [Co(CN)6]3-, oxidation state of Co is +3.
 7.82 Inorganic chemistry

co3+ ion
(3d6 4sO)
3d
Im
4s 4p 0„ the overall stability constant is related to thermodynamic
stability when the system has reached equilibrium. Stability

Co3+ ion in
[CO(CN)6]3- 44`
Im constants of few complexes in solution are given in the following
table.

system
+ Stabil onstantr++
d2sp3
SinceChpisastrongfieldligands,pairingof3delectrons Cu2++NH3=[Cuqul3)4]2+ 4.5 x loll
takes place, # = 0. Since inner cJ orbitals (3dy) are involved in
hybridisation (c72sp3), it is also known as low spin or irmer Cu2++4CN©=[Cu(CN)4]2~ 2.o x lo27

orbital complex. Age+ 4NH3 a [AgoJH3)2]® I.6 x 1o7

Co3++ 6NH3 a [C0quH3)6]3+ 5.o x 1o33

:%O[s6o]F-6];3s-'a"h£=h4s¥£e::a:pfrex[::::e¥#~;(%;):]}_ersc:
low spin complex. From the above values it is seen that CN° is a stronger ligand
than NH3.
7.14 STABILITY 0F COORDINATION
Important generalisations derived from the vast data on stability
COMPOUNDS IN SOLUTI0NS constants are as follows:
For the reaction, a. For a given metal and ligand the stability is generally greater,
[M(H20),.] + #L a [ML„] + #H20 ... (i) the greater the charge on the metal ion. Thus, stability of
The stability of the coordination compound [ML„] is measured coordination entities of ions of charge 3+ is greater than the
in terms of the overall stability constant (equilibrium constant) entities of 2 ions. Further, for the divalent ions of the first
given by the expression. row transition elements, irrespective of the ligand involved,
Pn = [ML„] / [M(H20)„] [L]" the stabilities vary in the Irving-Williams Order:
The above reaction, takes place in steps. Mn][ < Fell < Co[] <Ni[] < Cull < Zn[].
A coordination compound is formed in solution by the stepwise b. The metal ions, `class a' acceptors like metals of groups
addition of ligands to a metal ion. Thus formation of the complex, I and 2, the inner transition elements and the early
ML„ may be supposed to take place by the consecutive n steps. members of the transition series (groups 3 to 6) form their
[M(H20)„] + L = [ML(H20)„_i] + H20 most stable coordination entities with ligands containing N,
[ML(H20)"_l] 0 or F donor atoms.
K1-
[M(H20)"][L] c. The metal ions, `class b' acceptors like the transition

[ML(H20)„_i] + L a [ML(H20)„_2] + H20 elements-Rh, Pd, Ag, Ir, Au and Hg having relatively
full c7 orbitals form their most sable complexes with
[ML(H20)„_2]
K2- ligands whose donor/atoms are the heavier members of the
[M(H20)„_i][L]
N, 0 and F groups.
d. The stability also depends on the formation of chelate rings.
If L is an unidentate ligand and L-L, a didentate ligand and if
[ML„_1 (H20)] + L a [ML„] + H20
the donor atoms of L and L-L are the same element, then L-L
[MLJ will replace L. The stabilisation due to chelation is called the
K"
[ML„_, (H20)] [L] chelate effect. It is of great importance in biological systems
[M(H20)„] + #L = [ML„] + nH20 and analytical chemistry. The chelate effect is maximum
for the 5- and 6-membered rings. In general, rings provide
P„ = K] X K2 X K3 ... K„ = greater stability to the complex.
[M(H20)" [L]"
e. If a multidentate ligand happens to be cyclic and there are
By convention, the water, H20 displaced is ignored, as its
concentration remains essentially constant.
no unfavourable steric effects, a further increase in stability
occurs. This is termed the macrocyclic effect.
K], K2 ,... K„ are called stepwise stability constant. In general,
the values of successive stability constants decrease regularly
7.15 COLOUR IN COORDINATION
from K] to K„. P„ is called the overall stability constant (and 1/P„
is called as instability constant). The higher the overall stability COMPOUNDS
constant value of the complex, the more stable it is. Altematively, Coordination compounds of transition metal have fascinating
values called instability constant explain the dissociation of the colours. The study of the colour of transition metal complexes
complex into metal ion and ligands in the solution. can be divided into two categories:
 Coordination compounds 7.83

a. Colour of the complex ions whose central metal atom

cr2+ 3# („ -4) Blue
contains partially filled d-orbitals.
Mn3+ 3J1 („ - 4) Violet
When wllite light which is composed of many different
Mn2+ 3d5 ¢ - 5) Pink
colours falls on a coloured complex ion or complex
Fe3+ 3d5 (n - 5) Yellow
compound of a transition metal, the ion or complex absorbs
some portion of the white light and the remaining portion Fe2+ 3d6 (n - 4) Green
of the incident light is transimitted or reflected by the co2+ 3 drf (n ~- 5) Pink (red)
complex/ion. The colour of absorbed light and transmitted Ni2+ 3d8(n-2:) Blue green
are different from each other. The colour of the transmitted cu2+ 3d9 (n - 1) Blue
light is called complimentary colour of the adsorbed light,
Colours of transition metal ions in aqueous solution
given in Table 7.22. The complimentary colour is the colour
corresponds to their aqua complexes.
generated from the wavelength left over.
Following table gives the wavelength of light adsorbed and
Table 7.22 Colour of absorbed and transmitted radiations the coloured observed in some coordination entities.
Colourqfthi + ^Rangeof±he Colour of the
Table 7.24 Relationship between the wavelength of light
absorbed licht/ Waveleftgth (A) v transmitted light
` ' I radiation absorbed and the colour observed in some
®f the absorbed { omplimeutary
i light colduF.,dy,
f the absorbed coordination entities
,ight
Coard\ination u; ^wi#¢elenrih Colour+of + t®.four of
Violet 4000 - 4500 Yellow green entities•J|::i;;f,: `"-, Oflightr • ,ight . coordin a-
Blue 4500 -4800 Yellow absorbed + + absorbed tio`¢` entj!ty, J
`flm
Green blue 4800 - 4900 Orange
[COCIQVH3)5]2+ 535 Yellow Violet
Blue green 4900 - 5000 Red
[CoquH3)5(H20)]3+ 500 Blue green Red
Green 5000 - 5600 Violet (almost pulple)
[coavH3)6]3+ 475 Blue YellowOrange
Yellow green 5600 -5750 Viol'et
Yellow 5750 -5900 Blue
[co(cN,6]3- 310 Ultraviolet Paleyellow
Orange 5900 -6250 Green blue
Red `, 6250 -7500 Blue green [Cu(H20)4]2+ 600 Red Blue

For example: [Ti(H20)6]3+ 498 Blue green Puxple

i.HydratedCu2+ion,i.e.[Cu(H20)4]S04.H20orCuS04.5H20 The colour of the absorbed light also depends on
absorbs yellow radiation and transmits blue radiation and the nature of the ligands. For example, Ni2+ ion in
hence looks blue to our eyes.
ii. Hydrated Ti3+ ion, [Ti(H20)6]3+ absorbs green radiation #isT::)[6n]2[+N:bd°=:;6i?f[aonndahb:o::sh;:1:;uw[Link]r[Link]i;
therefore blue in colour. Thus, although the central metal ion
hence transmits the radiation of purple colour. Hydrated
is same in [Link] the complex ions, these ions absorb radiation
Ti3+ ion, therefore looks violet (almost purple).
of different colours and therefore have different colours.
iii. Anhydrous Co3+ compounds absorb the radiation of red
Energy associated with the wavelength of the radiation
colour and therefore appear blue green. Whereas, hydrated absorbed can be calculated as follows.
Co2+ioni.e.[Co(H20)6]2+ionabsorbsbluegreenradiation Let[M(H20)6]"+ionabsorbstheradiationofwavelengiv^A.
and therefore appears red. Thenthefrequencyorwavenumber(incm-I)corresponding
Colours of some common hexahydrated transition metal to this wavelength is given by
complex ions [M(H20)6]"+ are given in Table 7.23. Frequency v or wave number (in cm-I) of the absorbed
radiation of wave length of ^A.
Table 7.23 Colours of some common [M(H20)6]n+ ions 11

' C®toLI* of the ipn victct z,

rfu = A x io~8 cm
tonfigLlration r
.1o8
Ti3+ 3d` („ -I) Violet (almost purple)
i ( ..., A -,0-8 cm,
v3+ 3d2 (n - 2) Green This frequency is associated with energy whose magnitude
v2+' cr3+ 3d3 (" - 3) Violet canbecalculatedinkcalmol-]orkJmol-]byusingthefact
that
7.84 Inorganic chemistry

350 cm-I = 1 kcal mol-I Equation (iii) shows that

and 83.7 cm-I = I kJ mo|-I Energy associated with a wavelength of ^ A

lo8
1 kcal mol-I = ± cm-I kJ mol-I ... (iv)
83.7 x ^ (in A)
The above conversion is obtained by using the following
Equations (ii) and (iv) both show that the energy associated
relation:
with the absorbed radiation is inversely proportional to the
E
E--NAh c~v, -v-- wavelength of the radiation but directly proportional to the
N A.h c
frequency of the radiation.
where E = 1 kcal morL Explanation of the violet (purple) colour of octahedral
IVA = 6.02 x |o23 moi-I [Ti(H20)6]3+ionbydLde]ectrontransition.
fe = 6.6 x io-34 ]s The complex [Ti(H20)6]3+, which is violet in colour, is an
OR octahedral complex where the single electron (Ti3+ is a 3d'

6.6x|0-34xio-3
kcal :yastt::i;:ethceo:;fe'x?:rhte[t::ist£:]tghhee:tsg;[be[:es[t;antethaevg:aubn,:
4.18
fortheelectronistheempty`eg'[Link]
c = 3 x 108 ms-I = 3 x |08 x 102 cm s-I to the energy of yellow-green region is absorbed by the
complex, it would excite the electron from `t2g' level to the
1kcalmol-]x4.18
V= -35o cm-1
6.02x|023mo|-'x6.6x|o-34x|O-3kca|s ;;8;eL::seLv(Lt;[Link]=o:2:g):g:)riec:;Sset:refin::¥':£:oC;mt:Lues:
x3x|08x|02cms-I attributes the colour of the coordination compounds of dud
transition of the electron.
Therefore, I kcal mol-) = 350 cm-I
Energy
eg i-eg
| kJ mo|-I = + cm-I
The above conversion is obtained as follows:

E=NAhc-v ~v--
E
N A,h c
1 i - - t2g
Ground state
vvtw
Excited state

Fig. 7.47 Transition of an electron in [Ti(H20)6]3+

where E= 1kJmol-I
b. Colour of the complex ions whose central atom contains
IVA = 6.02 x 1023 mo|-I empty or comp]ete]y filled d-orbita]s.
The transition metal complex ions whose central atom
fo = 6.6 x |0-34 Ts = 6.6 x |o-34 x |o-3 k|s
contains empty (d° [Link]) or completely filled
c = 3 x |08ms-I = 3 x |08 x |o2 cms-I cJ-orbitals (d]° configuration) are coloureless. This is due

1 kJ mol-I to the fact that in such cases c7~cJ transition is not possible.
Thus [Sc(H20)6]3+ (d[ system), [Ti(H20)6]4+, (# system),
6.o2 x io23 morl x 6.6 x io-34 x io-3 kTs
x 3.x |o8 x io2 cms-1 [Cu(H20)6]®, [Zn(H20)6]2+ (d'° system) are colourless.

= 83.7 cm-1
7.16 0RGANOMETALLIC
Therefore, 1 kJ mo[-) = 83.7 cm-I COMPOUNDS
Thus, since 350 cm-I = 1 kca| mo|-I Organometallic compounds are the compounds which contain at
108 _.__-1 _ 1o8
least one metal carbon bond. They also include the compounds
I Cm -= kcal mol-I ... (i) in which C-atom is bonded not only to metal atom but also to
A ---- 350 x A (in A)
metalloids (i.e., element less EN than carbon) e.g., boron (8)
Equation (i) shows that silicon (Si), arsenic (As) and tellurium (Te).
Energy ass_ociated with a wavelength of A A However, they are not confined to this definition or to their
lo8 name. Compounds like carbides, cyanides, carbonates and
kcal mol-I ... (ii)
350 x ^ (in A) carbonyls, though they contain metalutarbon bonds are not
Similarly, since 83.7. cm-I = 1 kJ mol-) considered as organometallic compounds by convention, because
their properties are much different than those of other compounds
1o8 1o8
- ^cm-I
'."
= 83.7x^(inA)
kJ mol-I ... (iii) [Link],
K2[Zn(CN)4]and[Ni(CO)4],arecoordinationcompoundsbutnot
 Coordination compounds 7.85

an organometallic. multicentre two electron bonds. The structures of some

Morever, although a compound may contain many hydrocarbon representative main group organometallic compounds are
radical, it is not classified as organometallic when its all the shown in Fig. 7.48.
C-atoms are linked to metal through atoms like 0, N or S as in
trimethyl orthoborate, B(OCH3)3, i.e. H3C-o-B<:::;
Which is thus not considered as organometallic compounds
since no C-atom is directly linked to boron (8).
But CH3B(OCH3)2 is an organometallic compound since it

containsatleastoneBlbondl.e.,H3C-B<::=:
Li4(CH3)4
Similarly (C3H70)4Ti is also not an organometallic compound
but C6H5Ti(OC3H7)3 is because it ihas one Til bond. (a)

1. Likewise diehtyl zinc, (C2H5)2Zn is an organometallic

compound in which two ethyl groups are directly linked
with Zn forming ZnT{ bonds.
:::>Al<:::>A1<:::
A12(CH3)6
2. Organometallic compounds containing either the
hydrocarbon radicals attached to the metal such as (C2H5)4 (b)

Pb or containing hydrocarbori radicals along with H atoms

1800
attached to the metal such as (CH3)3SiH are called Simple
organometallic compounds whereas those containing at
H3CJfuH3C
Me=Be or Mg
leastbnehydrocarbonradicalalongwithsomeothersgroups
attached to metal such as R-Mg-X and (C4H9)2Snc12 are (c)

called mixed organometallic compounds.

9H3
3. Organometallic compounds are not found in the nature.
H3C`:ZS[\CH3
7.16.1 CLASSIFICATION OF ORGANOMETALLIC
H3H3
COMPOUNDS
Based on the nature of Ml bond, they are broadly classified Me=Be or Mg Si(CH3)4

into two types as follows: (d) (e)

a. a-bonded organometauic compounds of the main groups

(s and p block) elements: These are covalent compounds
with (M{) a bonds in which bonding consists of localised HTc,fhe3
(M{) a bonds formed by sharing of an electrons pairs. CH3
The s- and p-block organometallics are named according AS(CH3)3
to the substituent names used in organic chemistry. For nB]

example methylithium for CH3Li and trimethylboron Fig.7.48Strugrugrae:o°iest°aT„9cr:oP:eps:##.Vemaingroup

for B(CH3)3 which is also called trimethylborane, taking
it to be a derivative of its hydrogen counterpart. Thus, Theirstructureshavebeenrepresentedbyempiricalfomulas
Si(CH3)4 [(Fig. 7.48(e)] and AS(CH3)3 [Fig. 7.48(I)] are though their actual structures are complex.
tetramethylsilane and trimethylarsane respectively. For example, (CH3)2Be and (CH3)2Mg have bridge
The oxidation number of the metallic element in an structures as represented in Fig. 7.48 (c and d).
organometallic compound is based on the organic moiety Similarly CH3Li (methyl lithium) exists as tetramer.
being considered to be anionic. For example, in Zn(CH3)2 Likewise, (CH3)3A1 (trimethyl aluminium) exists as a diner
andCH3groupistakentobenegativelycharged(1-).Thus, in which two methyl groups acts as bridges between two
oxidation number of zinc is 2+. The bond in alkyls of s-block Al-atoms as shown in Fig. 7.48®).
elements is highly polar (M6+{try in the organometallic
Organometallic compounds of electropositive metals are
compounds of groups 14,15 and 16, the M{ bonds are
strong reducing agents. They are pyrophoric and ignite
of relatively lower polarity. Methyl compounds of Li, Na,
spontaneously in air.
Be, Mg and Al are associated through alkyl bridges and

E
7.86 Inorganic chemistry

b. I. 7t-bonded organometallic compounds of d and Note: In these compounds the ^number following
f-block elements - 7t complexes: Transition metals ti~(eta,theGreekword)representsthenumberofc~atoms
form organometallic compounds of this type. The bound to the metal in the compound.
formation of these compounds cannot be explained in
2. Sandwich compounds (Ferrocene and dibenzene
terms of simple covalent bonding.
chromium).
Zeise's salt: The compound trichloridoetheneplatinate
i. The synthesis of highly stable compound Ferrocene
(11),[Ptc13(C2H4)]°hasthestructureshowninFig.7.49.
[bis-(cyclopentadienyl) iron(II)] or [Fe(T|5{5H5)2]
c\-:.-z8:: Cl. .,c (Fig. 7.50) in 1951 was a land mark in the
advancement of modem organometallic chemistry.
Pt- ,
It is called sandwich compound.
ck{--*cl C1

Fig. 7.49 Structures of Zeise's salt [PtcL3(q2-C2H4)]©

BAN of Ferrocene

Number of electrons = 6

Number of electrons = 24

Number of electrons = 6

BAN = 36 electrons

HAN rule is valid (a) (b) (c) (d)

fig. 7.50 (a-d) Structure of metallocene, Ferrocene [Fe(C5H5)2] (OR) [Fe(n5-C5H5)2]

Note: T`5 represents the number of c-atoms bond to the metal, i.e. 5{-atoms.

ii. Ferrocene is composed of Fe2+ sandwiched between EAN of Dibenzene chromium

two cyclopentadienyl anions and held together by
7t-complexation. There are no (C-Fe) a-bonds, as Number of
evidencedbythefactthatthetworingsfreelyrotate. electrons = 6
The most stable conformation is a staggered one with
the rings not flush.
Number of
iii. Ferrocene is stable because its Fe+2 has a full shell
electrons = 24
of 18 electrons, six of its own ®resent in its five 3d
atomic orbitals) and six from each cyclopentadienyl
Number of
anion. It also retains the aromaticity of the each
electrons = 6
cyclopentadienyl anions.
iv. Many transition metals form sandwich compounds EAN = 36 electrons AN rule is valid
with aromatic compounds providing the
fig. 7.51 Structure of dibenzene chromium [Cr(T`6-Col+6)2]
combined number of valence shell electrons is 18,
e.g. dibenzenechromium [Cr(C6H6)2] Or 3. f-Block organometallic compound: In late l970s, the
[Cr(116-C6H6)2], six from Cr, and six from each firstf-blockorganometalliccompoundwasprepared,e.g.
benzene. [Th+4 IT[ (OR)-1 [n5 ~ C5Me5)2] or Alkoxohydridobis
 Coordination compounds 7.87

®entanethylcyclopentadienyl) thorium (IV) (Fig. 7.52) part of the d block form stable, neutral binary carbonyls like:
theligandC5Me5,i.e.,pentamethylcyclopentadienylion
[V (CO)6], [Cr(CO)6], [MO(CO)6], [W(CO)6 ], [Mn2 (CO)[o],
forms stable f-block compounds.
[Fe(CO)5], [Fe2(CO)9 ], [C02(CO)8], [C04 (CO)i2] [Ni(CO)4],
etc. Outside the central part of d-block, the metal carbonyls are
usually unstable.

7.17.1 CARBONYLS-STRUCTURE AND BONDING

Homoleptic binary metal carbonyls have simple, well-defined
structures.
Tetracarbonylnickel(0) is trtrahedral, pentacarbonyliron(o)
is trigonal bipyramidal while hexacarbonylchromium(o) is
octahedral. Decarbonyldimanganese(o) is made up of two
square pyramidal Mn(CO)5 unit joined by a Mn-Mn bond.
Octacarbonyldicobalt(o) has a Co-Co bond bridged by two CO
groups (Fig. 7.54).

(a) co\dr./co
Co/T'\co
CO
co-k:
Lcuo/
/
COCO
CO I
J4n/i:uco
,cO

Fig. 7.52 (a-b) Structure of [Th H (OR) (n5-C5Me5)2]

co co
co/ co
7.16.2 BONDING OF ALI{ENES TO A TRANSITION
Cr(CO)6 [Mn2(CO) I o]
METAL
Octahedral
According to Dewar, the metal to alkene bond consists of two parts:
i. Overlap of the filled 7t-orbital of the alkene with an acceptor
foco
vacant d-orbital on the metal atom when a-donation from
filled 7t-orbital of alkene into vacant d-orbital on the metal c\:¥i':<:: :`c:.±ie&ie2..:a::
O=C: Fe+:c=O
OCcurs. \e:o`.b``o
ii. 7t back donation from a filled d-orbital on the metal into
C02(CO)8
a,c. rT|_ /,i,\\ I
vacant antibonding orbital of alkene. Thus according to this [Fe2(CO)9]
view, the metal~alkene bond involves some double bond

\/\/
character Fig. 7.53(a and b).

C__C
Fig. 7.54 Structure of some representative liomoLeptic metal

7.17.2 PROPERTIES OF METAL CARBONYLS

OMCE>+es i. Most of the metal carbonyls are solids at room temperature

/\/\
CC

Fig.7.53(a)0-d:nv::aonntfdr?o#tL:#np-tohrebi:aeLtsa?ftheaLkeneinto
and atmospheric pressure. The only exceptions are nickel
and iron carbonyls which are liquids.
ii. Mononuclear carbonyls are volatile and toxic. Further,
they are either colourless or they have a light colour. For
exampleFe(CO)[Link]
hand,polynuclearcarbonylshaveadeepcolour.Fe3(CO)]2,

§Mg+°Y°_§MGS dodecarcarbonyl triiron(0), for example is a deep grass green

solid.

G es a,t\cD 'G--es22 iii. They [Link] in hydrocarbon solvents, the only exception
being Fe2 (CO)9, i.e., enneacarbonyl diiron(0).
fig.7.53(b)n#:Cvkafa°nnta=n°tiTbfor:Ffnagfi;Lr';fdtad,-:fbafi#enthemeta"nt° iv. Their reactivity is partly due to the central (metal atom and
partly due to the CO ligands.

7.17 METAL CARB0NYLS 7.17.3 USES OF METAL CATALYSTS

Awidelystudiedandimportantclassoforganometalliccompounds i. They are used as industrial catalysts.
is that of metal carbonyls. The homoleptic carbonyls (compounds ii. They are used as precursors in synthesis of organic
containing carbonyl ligands only) are formed by most of the
compounds.
transition metals (d metals). The metals constituting the central
7.88 Inorganic chemistry

7.17.4 BONDING IN METAL CARBONYLS ii. Reaction between ethylenediamine (en) and ptc12 gives
The metalrf arbon bonds in metal carbonyls have both a and 7t pr(en)2]cl2.
character. The formation of bonds between the metal and carbon Nic12 + 2 en - pr(en)2]C12
atom of carbon monoxide is described below.
2. Substitution reactions: Most of the coordination
compounds are prepared by this method. In this meinod
orb::aeL::S:h°ev::iabponfaieosn:Lxa£Cdeeb;Th[Link]h=pfi;Lefe:a°Ln£:::b:ta=
stronger ligands replace the weaker ligands. For example,
resulting in a a-bond between the metal and carbon atom of carbon
monoxide. Here, donation of lone pair of electrons on carbon into [Cu(N113)4]2+complexioninpreparedbyheatingaqucous
a vacant d-orbital of the metal takes place. As CO is a weak base/ copper sulphate solution with ammonia.
weak donor, the a-bond forined with the metal atom is weak.
[Cu(H20)4]2++4NH3-[Cu(N113)4]2++4H20
7t*
•--,/,/,,'' In this case, NH3 molecules replace the water moleoules
(weaker ligands) surrounding the Cu2+ ion.
3. Redox reactions: By this method, a complex with the

€.S .€
Fj(gb.)7#vce!ri:tpi:#!i:tL:.I:[Link]:°f¥jL:&nreo:i!::irTo?eLfp::#L:°§doeie:i:i#d::°!nb:--ab:I::€¥t:n:a
metal atom in a higher oxidation state than in the starting
material is obtained by carrying out the process of complex
formation in the presence of an oxidising agent e.g. H202
or perchlorates. For example pentraamminitratocobalt (Ill)
vacant antibonding 7[*-orl)itaL of CO, i.e., formation of (M-C) 7t bond nitrate [Co(N03)(N113)5] qu03)2 is prepared by adding
concentrated solution of ammonia containing NH4N03 to
The second overlap takes place between the filled metal d-orbital
cobalt (11) nitrate solution in the presence of H202.

refst:it::gei::?di::;ibaT:di::d"3Pe*£;rebeLia:h:f:::ale:nbd°sna:e°::rxb]:: 2[Coqo)6] OV03)2 + 8NH3 + 2NH4N03 + H2021

monoxide molecule. Here, donation of electrons from a filled metal
2[cO(No3) (N113)5] oro3)2 + 14H2o
d-orbital into a vacant antibonding 7t*-orbital of co occurs (back
bonding). Here, CO is acting as an acceptor ligand. Similarly, hexaammininecobalt (Ill) chloride can be
The effect of a bond formation strengthens 7t bond and vice
prepared by adding ammonium chloride to the aqueous
versa. This is called synergic effect (i.e., working together towards solution of cobalt chloride made alkaline with ammonia in
the same goal). Thus, as a result of synergic effect, the bond
the presence of H202.
between CO and metal is strengthened.
Further, as explained above, a weak a bond is formed by 2CoC12 + 2NH4C1 + 10NH3 + H202 -
donation of electron pair from carbon to metal (M+C=0) and 2[COOu3)6] C13 + 2H20
a stronger 7t bond (second bond) is formed by back donation of
electrons from filled d-orbital of metal into empty antibonding a. Preparation of a-bonded organometallic
7t* orbital of carbon (7t M + C bond). [Link] bonding is thus compounds:
M = C = C). Thus, bond order of C - 0) bond is reduced from i. Organoalkali compounds and Grignard reagents:
triple bond to double bond. This is supported by the fact that These are obtained directly by the reaction between
C -0) bond length in C = 0 is 128 A and it increases to about an alkyl halide and metal e.g.,
1.15 A in many carbonyls.
R_x+2M ether >R_M+Mx
Ligands such as CO which are capable of accepting an
appreciable amount of electron density from the metal atom into R_x+Mg ether >R_M_MX
empty 7t or 7t* orbital of their own are called 7t-acceptor or 7t-acid qu = Li, Na, K, X = Cl, Br, I)
ligands.
ii. Tetraalkyl tin and tetraalkyl lead: These
are obtained by reaction of metal halide with
7.18 PREPARATION OF onganometallic compound.
COORDINATION COMPOUNDS Snc14 + 4BULi - Bu4Sn + 4LicI
Coordination compounds are prepared by the following general Butyl lithium Tetrabutyl tin
methods of preparation:
I. Direct combination of reactants: Under suitable Pbc14 + 4EtMgBr - Et4Pb + 4MgBrcI
conditions, the reactants are made to react in requisite Ethyl mag bromide Tetraethyl

molecular proportion to produce coordination compounds. (G.R.) lead (TEL)

For example, Tetraethyl lead (TEL) which is an important

i. Metal ammines can be obtained by the direct reaction anti-knocking agent is prepared commercially by
between a metal salt and liquid ammonia, reaction of ethyl iodide with lead sodium alloy.

Nic12(S) + 6NH3(I) - INiovH3)6]C12

4C2H5I + 4 PbINa - (C2H5)4Pb + 4Nal + 3Pb
 Coordination compounds 7.89

b. Preparation of 7[ngomplexes:
i. Preparation ofzeise's salt: It is obtained by direct
raplacementoftheweakerCl©ligandof[Ptc14]2- ::>p<:
complex ion by ethylene on heating. Cis-platin
K2[Ptc14]+CH2=CH24K3[Ptc13(C2H4)]+KCI [Anti-cancer agent]
(a)
Zeise's salt
Active
ii. Preparation of ferrocene: It is obtained by the
site
following reaction:
2C5H5M8Br + FecL - [(C5H5)2Fe] + 2MgBrcI
Ferrocene
iii. Preparation of dibenzene chromiuln: It is obtained
by heating benzene with chromium vapours:
2C6H6 + Cr (Vapour) - [(C6H6)2Cr]
c. Preparation of metal carbonyls: Metal carbonyls " P°rtion of e``r `
are obtained by direct reaction between the metal and
Carboxypeptidase-A
cardon monoxide under appropriate condition e.g.,
(b)
Ni + 4co R°°mTemp. > INi(C04)]
Nickel tetracarbonyl i2 > Central metal atom (CMA) = Co2+

Fe+5CO¥ITe(CO)5] I: igand = Corrin

(c)
Iron pentacarbonyl
8 found in haemoglobin and myoglobin.
The reaction between nickel and carbon monoxide to metal atom (CMA) = Fe2+
form volatile compounds which decomposes easily to = Poaphyrin
[:I:gn:tr:::
give back nickel is used for the purification of nickel.
The method is known as Mond's process.

7.19 IMPORTANCEANDAPPLICATIONS [:]hg[:::P=h¥]:£ahaynrfnb)Cen::I)metalatom(CMA)=Mg2+]

(e)
OF COORDINATloN
Structures of some important compounds
COMPOUNDS/COMPLEXES
2. In analytical chemistry:
The importance of coordination compounds in various fields is
a. In qualitative analysis: In salt analysis, the presence of
discussed below:
a number of basic radicals is confirmed by converting
I. In biological systems: them into suitable complexes which are coloured. For
a. Coordination compounds are of great importance in example
biological systems. Familiar examples being: i. Fe2+ and Fe3+ ions are tested and distinguished by

i. Chlorophylls (the green pigments in plants, central potassium ferrocyanide K4[Fe(CN)6] and potassiuln
ferricyanide K3[Fe(CN)6] as shown below:
to photosyntyhesis).
keiserlt , .' Fe-
ii. Haemoglobin (the redpigment ofblood, which acts
i. [Fe2+(CN)6]4~ Fe22+[Fe2+(CN)6]4~ Fe43+[Fe2+(CN)6]34- t
as oxygen carrier) along with myoglobin (which
Ferrocyanide Ferro-ferro eyanide Ferri-ferro cyanide
store.s oxygen and is a regulator of respiration).
ion (white ppt) (Puns sion blue)
iii. Vitamin B ) 2 cyanocobalammine, the anti-pemacious
ii. [Fe3+(CN)6]3- Fe32+rFe3+(CN)6]2- Fe3+[Fe3+(CN)6]3-
anaemia factor. Ferricyanide Ferrorferri cyanide F erri-fein cyanide
All of these, respectively, are the coordination ion (Tunbull's blue) (Brown solution)
compounds of magnesium, iron and cobalt with the
macrocyclic poxphyrin and corrin ligands.
b. Among the other compounds of biological importance
with coordinated metal ions are the enzymes like,
carboxypeptides A and carbonic anhydrase (catalysts
of biological system) (Figure).
7.90 Inorganic chemistry

ii. Fe3+ ions are also detected by adding thiocyanate the same conditions, one of the metal ions may
ions (from ammonium thiocyanate) when a blood form a soluble complex while the other may form
red colouration is obtained due to the fomation of as insoluble complex.
a complex i.e. ferrithiocyanate. For example, with ammonium or potassium
Fe3++ 3CNS° -Fe(CNS)3 ferrocyanide solution, Co2+ ion forms an insoluble
Thiocyanate Ferrithiocyanate complex while Ni2+ ion forms similar complex but
ion @lood red colour)
soluble in NH40H.
iii. Zn2+ ions are tested by adding potassium
ferrocyanide solution to the acidified salt solution i. Co2+ + [Fe(CN)6]4--Co2[Fe(CN)6]
when a bluish white precipitate is obtained due Insoluble in NH40H

to formation of a complex i.e., zinc ferrocyanide

ii. Ni2+ + [Fe(cN)6r -Ni2[Fe(cN)6]
or zinc hexacyanoferrate (11).
Soluble in NH40H
2Znc12 + K4[Fe(CN)6] -Zn2[Fe(CN)6] + 4KCI
Zinc hexacyano 3. Colour of metal ions witll chelating ligands: There are
ferrate(II) many examples of the use of coordination compounds in
(Bluish white ppt.)
qualitative and quantitative chemical analysis. The familiar
OR colourreactiongivenbymetalionswithanumberofligands
Zn2+ + [Fe2+(CN)6]4- -Zn2[Fe(CN)6] (especially the chelating ligands as a result of formation of
iv. Cu2+ ions are tested I)y adding potassium coordination entities, fomi the basis for their detection and
ferrocyanide solution to the acidified salt solution estimationbyclassicalandinstrunentalmethodsofanalysis.
when a chocolate colour precipitate is obtained due Most of these reactions are highly specific and sensitive
to formation of a complex i.e. , copper ferrocyanide under controlled experimental conditions. Often the
or copper hexacyanoferrate (11). detection/estimation limits tend to parts per million (ppm),
Cu2+ + [Fe(CN)6]4- - Cu2[Fe(CN)6] or even parts per billion (ppb) levels.
Chocolate colour precipitate Familiar examples of such reagents are as follows:
v. a. Thepresence ofco2+ion is testedbypotassium dimethylglyoxime , Ch-nitroso -P -naphthol ,
[Link] test when a reddish brown 8-hydroxyquinoline,1,10-phenanthroline (ph), benzoin
precipitate is obtained due to the formation of oxime (i.e. cupron), as given in following Table 7.25.
an insoluble complex.
Table 7.25 Colour of metal ions with chelating (organic)
3CoC12 + 3K3[Fe(CN)6] ±£± C03[Fe(CN)6]2 + 6KCI reagents
Potas sium C ob alt hexacyano •. :, ,del*ur
rerricyanide ferrate (Ill) Metal |JontobE
(reddish broun ppt.) ;?,a;:J<`:':5_#r",|g,: re@g€nt§ used \ ae
OR estimated+ •(,, - --,i ,i "? -- !

3Co2++[Fe3+(CN)6]3-=±±C03[Fe(CN)6]2
I, Ni2+ Red 9-10 Dimethylglyoxime

b. Co2+ ions are also tested by adding ammonium ii. co2+ Redprecipitate c»-Nitroso-P-naphihol
thiocyanate solution when a blue colour is
obtained due to formation of a complex. iii. A13+ Blue 8-hydroxyquinoline
CoC12+NH4SCN=SCo(SCN)2+2NH4C1 (Oxine)

NH4SCN iv. Fe3+ Brown I,10-Phenanthroline

j ®h)
oun4)2[cO(SCN)4]
Ammonium tetrathio- V, cu2+ Red 9-10 Benzoin oxime
cyanatocobaltate(II)
(i.e. , cupron)
Glue colour)
OR Note: In arrmonical
co2++2sCNe-[Co(SCN)2]2E££[Co(SCN)4]2- forms yellow

vi. Separation of mixture of two ions: A mixture of i. Ni2+ ions: The presence ofNi2+ ion is detected by adding
two ions can be separated also. Some reagent under dimethyl glyoxime in the presence of NH40H (at pH =
 Coordination compounds 7.91

9-10) to the salt solution, a red ppt. is formed, due to

formation of a complex.

2(=::]=::=)+Ni2++28HJEi
Dimethylglyoxime

+ 2H20

Nickel dimethyl glyoxime complex (red ppt.)

ii. The presence of Co2+ ion is detected by adding

Ch-nitroso-P-naphthol to the salt solution, a red ppt. is v. The presence of Cu2+ ion is detected by adding
formed due to the formation of a complex. benzoin oxime (also called as cuperon) in the presence
of NH40H (at pH = 9-10) to the salt solution, a red
O-N: precipitate is formed due to the formation of a complex.
[Link]
I

[Link]
a-nitroso-a-naphtho1
OH-------

2H20 +
::I::=cu <E=:
JI
0-------HO
Red precipitate
Red precipitate
4. In quantitative analysis (estimations):
i. Gravimetric analysis: The amount of metal present
iii. A13+: The presence of A13+ ion is detected by adding
in a given sample can be estimated by converting a
8-hydroxyquinoline to the salt solution, a blue
known amount of the sample into an insoluble complex
precipitate is fomed due to the formation of a complex.
which can be filtered, dried and weighed. For example,
the amount of nickel present in a salt is estimated by

2(8.H) + A13+
precipitating it as nickel dimethyl glyoxime complex.
ii. Volumetric analysis (complexometric titrations): A
number of metal ions react completely with polydentate
8-hydroxy-quinoline ligands at an appropriate pH to form complexes. Hence,
the solutions of metal ions can be titrated against the
solutions of the polydentate ligands in the presence of a
buffer OVH40H + NH4Cl) at-pH = 10 and the end point
canbedetectedbyusingasuitableindicator(eriochrome
black-T). The colour must be wine red at this stage.
The colour at the end point is blue. The most common
Blue precipitate polydentate ligand used is ethylene diamine tetraacetic
acid (EDTA) is as given.
iv. Fe3+: The presence of Fe3+ ion is detected by adding
1,10-phenanthroline ®h) to the salt solution, a brown
precipitate is formed due to the formation of a complex. ::::=:::>N-CH2-H2-N<:=:::::
7.92 Inorganic chemistry

It is a hexadentate ligand and it coordinates through 2K[Au(CN)2] + Zn - K2 [Zn(CN)4] + 2Au

two N~atoms and four O-atoms of the |OOH groups. 6. In purification of metals: Some metals are purified
It is usually represented by H4Y. Its disodium salt is by formation of their metal carbonyls followed by their
commonly used because of its better solubility in water. decomposition, e.g. , impure nickel is converted into nickel
Its formula is represented as Na2H2Y. It ionises as tetracarbonyl Ni(CO)4 which on decompositon gives pure
Na2H2Y-2Na©+H2Y2- nickel. This method is known as Mond's process.
The reactions of the metal ions like Ca2+, Mg2+, 7. In industry:
Zn2+ ions etc. (in general, M2+) with EDTA may be a. As catalysts: Coordination compounds are used as
represented as follows: catalysts for many industrial processes. A few examples
M2++H2Y2-=MY2-+2H® are given below:
The indicators most commonly used are organic dyes i. Homogeneous catalysis: Wilkinson catalysts,
such as Eriochrome black-T or Calcon. with the formula, [Rhcl (Ph3P)3], i.e., chloridotris
Thehardnessofwaterduetopresenceofca2+andMg2+ (triphenyl) phosphine rhodium (I), is used for
ions is estimated by these complexometric titration. selective hydrogenation of alkene. The double

iii. In meta]]urgy (extraction of metals): The noble bond at the end of the chain is hydrogenated but

metals like silver (Ag) and gold (Au) are extracted from the double bonds elsewhere in the chain are not

their ores through the fomation of cyanide complexes affected. Moreover, Wilkinson catalyst (WC) also
reduces carboxylic acids (RCOOH) to alcohols
[Ag(CN)2]©[Au(CN)2]®respectively.
(RCH20H), e.g.,
a. Extraction of silver (Ag): Silver is extracted from
its ore by first dissolving the ore in NacN solution CH3CH2CH=CH2¥SiCH3CH2CH2CH3
and then precipitating out silver by adding more
CH3CH=CELCH3|Noreaction
reactive electropositive metal, zinc (Zn).
i. Ag2S + 4NacN = 2Na[Ag(CN)2] + Na2S
CH3COOH¥H3OuH20H
Sodium dicyano
ii. Heterogeneous catalysis: Ziegler-Natta
argentate (I) catalyst is used as heterogeneous catalysts, e.g.,
triethylaluminium [(C2H5)3Al] and titanium
Zn
1 tetrachloride (Tic14). It is used as a catalyst for the
Na2[Zn(CN)4] + 2Ag
low temperature polymerisation of alkene i.e., for
OR the synthesis of HDPE (high density polyethene)
ii. 4Ag® + 4CN©-2[Ag(CN)2]® from ethene.
b. In electroplating: Articles ca.n be electroplated
Zn
1 with silver or gold much more smoothly and evenly
[Zn2+(CN4-)4]2-+2Ag from solutions of the complexes [Ag(CN)2]° and
iii. Native silver (Ag) also dissolve in NacN [Au (CN)2]° than from the solutions of simple metal
solution in the presence of 02 in air. Silver is ions.
precipitated by addition of scrap zinc (Zn). c. In photography: The developed film is fixedby washing
4Ag + 8NacN + 02 (from air) + 2H20 with hypo solution which dissolves the undecomposed

Zn
AgBr to form a complex.
j A8Br + 2Na2S203 -Na3[Ag(S203)2] + NaBr
Na2[Zn(CN)4] + 2Ag ZL 4Na[Ag(CN)2] + 4NaoH
Sod. dithiosuiphato
argentate (I)
b. Extraction of gold (Au): The cyanide process used
for the extraction of gold is based upon the fact that d. As dyes or pigments: Phthalocyanine blue which is an
gold dissolves in KCN solution in the presence extremely stable complcx of copper (11) is one of the
of atmospheric oxygen to fom a soluble cyanide many complex compounds used as dyes or pigments.
complex
8. In medical field: The well-known examples are given
4Au + 8KCN + 2H20 + 02(air) - below:
4K[Au(CN)2] + 4 KOH
i. British anti-Lewisite (BAL) in which the chelating agent
From the complex cyanide solution, gold is
is HSCH2CH(SH)CH20H was developed during war
precipitated out by adding zinc scraps.
time as an antidote to an arsenic containing poisonous
 Coordination compounds 7.93

gas (Lewisite). BAL is now used to treat poisoning by 10. Organic synthesis: They are widely used in the synthesis
As, Hg, Au, Bi, Sb and even Pb and Cd. of various types of organic compounds, e.g. , organolithium
and organomagnesium compounds (Grignard reagent) are
ii. Calcium salt of EDTA is quite often used for treatment
commonlyusedforthesynthesisofdifferenttypesoforganic
of lead poisoning and dermatitis and poisoning by Cr
compounds.
or Ni.
11. Future applications: It is expected that the organometallic
iii. Metals present in toxic proportions in animals and compounds will find an important role in the production of
plants are removed by chelate therapy, e.g., excess ol semiconductors for the electronic industry, pharmaceuticals ,
copper and iron are removed by using chelating ligands, flavours and fragrances.
D-penicillamine and desferrioxime-B ,
iv. Recently, the platinum complex, CZ.S [Pt(NH3)2C12],
known as cisplatin has been found to be useful in the
I. Find out the total number of compound(s) which is/are
treatment of cancer (tumours). Its structure is as follows: diamagnetic in nature according to CFT.
I. Na3[Cr(OX)3] 11. Na3[CO(CN)6]

::>pt<: Ill. CaINiBr4]

V. C102
IV. C120
VI. CIO?
cz's-platin VII. C1207.
[chti-canc er agent] 2. Calculate total C.F.S.E. in term of Dq for the complex
prnc16]3- and [FeBr6]4-
This compound has the ability to block the uncontrolled
division of cancerous cells that results in the growth of 3. If I = C.F.S.E. value of light pink coloured compound
tumours. Recent studies show that ci.s-platin can cause formed when KMn04 is reduced by acidified H2S.
serious side effect, including severe kidney damage. )/ = C.F.S.E. value of light-pink coloured compound (A)
Therefore now-a-days cz.s-platin has been replaced by formed is the reaction.
Pb304/dil.HN03
the following compound. A (Light pink colour complex)
H3N\p,,C1
HMn0412S4±i+A(Lightpinkcolourcompound)
`NH2-(CH2)n-H2N''.`NH3
3Cj>pt<NNIH:
[ Then calculate the value of a -}j).
4. C.F.S.E. for [Co(H20)6]2+ is 6400 cm-I, pairing energy
fr¢#s-isomer (# = 2 to 6)

v. Anumber oforganoarsenic compounds are used as main for Co2+ is 20,000 cm-i, then calculate the value of 4g-
1o3
remedy for syphilis. in cm-I .
vi. The modem surgery makes use of silicon rubbers for 5. Ifx = number of 7t-bonds in ferrocene
spare parts in the body. y = Number of 7[-bonds in zeise's salt
vii. Silicon rubbers are also used as cosmetic surgery. z = Number of 7t-bonds is dibenzene chromium.
9. In agriculture: To prevent infectioh of young plants, the Then (x + )/) ~ z is:
seeds are treated with organometallic compounds such as 6. Calculate the total number of a, 7t and 8-bond in the
ethyl mercury iodide (C2H5HgI). complex anion [Re2Br8]2-
7.94 Inorganic chemistry

Exerc].ses
9. Coordination number of calcium is six in:
( 1 ) [Mg(EDTA)]2- (2) Mgc204
Naming, Terminology and Ligands (3) [M8(C204)2]2- d. M8S04.4H20
1. Select the correct IUPAC name for 10. Coordination number of cu2+ in CuS04.5H20 is
[Ti (7t -C5H5)2 (OiJ5H5)2]: (1) 5 (2)4

( 1 ) bis (T`5-cyclopentadiene) bis (cyclopentadiene) (3) 3 (4)2

titanate(IV) 11. The closed ring compounds formed by bidentate ligands, on
(2) bis (115-cyclopentadienyl) bis (cyclopentadienyl) binding to a metal or metal ions are called:
titanium(IV) ( l ) Monodentate (2) Chelates
(3) bis (cyclopentadienyl) bis (Ti5- cyclopentadienyl) (3) Ambidentate (4) None of these
titanate(IV) 12. Which is the pair of ambidentate ligand?
(4) bis (Ti 5-cyclopentadiene) bis (cyclopentadiene) (1) CN©, N09 (2) No3°, SCN°
titanium(IV)
(3) N3©, N02e (4) NCS©, C202-
2. Select the correct IUPAC name for
13. Number ofwatermolecules acting as ligands in cus04. 5H20,
[MO(a-C3H5) (7ti5H5) (C03)]
Zns04.5H20, Fes04.7H20 respectively are
( 1 ) Tricarbonyl (Ti 5-cyclopentadienyl) allyl molybdate(II)
(1)5,5,7 (2)4,5,4
(2) Allytricarbonyl (Ti 5-cyclopentadiene) molybdate(II)
(3)4, 4, 6 (4)4, 4, 7
(3) Allyltricarbonyl (115-cyclopentadienyl) molybdenum(II)
14. Select the correct IUPAC name for
(4) Allyl tricarbonyl (n5-cyclopentadienyl) molybdenum(II)
3. IUPAC name for [Fe(CO)2(a-C5H5) (7t-C5H5)] Complex: [Pt(C5H5N)4] [Ptc14] Complex:
( I ) Tetrapyridineplatinate(II) tetrachloridoplatinate(II)
. ( I ) Dicarbonyl (Ti 5-cyclopentadienyl) (cyclopentadienyl)
ferrate(II) (2) Tetrapyridineplatinate (II) tetrachloridoplatinate(II)
(2) Dicarbonyl (T`5-cyclopentadiene) (cyclopentadienyl) (3 ) Tetrapyridineplatinate(II) tetrachloridop latinum(II)
iron(II)
(4) Tetrapyri dineplatinum(II) tetrachloridop latinate (II)
(3) Dicarbonyl (n5-cyclopentadienyl) (cyclopentadienyl) 15. Select the correct IUPAC name for [C4H4Fe(CO)3] Complex:
iron(II)
(1)ti4-cyclebutadienetricarbonyliron(0)
(4) Dicarbonyl (n5-cyclopentadienyl) (Ti 5-cyclopentadienyl)
iron(II) (2) Tricarbonyl (114-cyclobutadienyl) iron(0)
4. Select the correct IUPAC name for [Cr(C6H6)(CO)3]: (3 ) Tricarbonyl (ti4-cyclobutadiene) iron( 1 )

( 1 ) (n6-benzene) tricarbonylchromate(0) (4) Tricarbonyl (T`4-cyclobutadiene) iron(0)

(2) Tricarbonyl (116-benzene)chromate(0) 16. Oxidation state of "V" in Rb4K[Hvio028] is
(3) Tricarbonyl (Ti6-benzene)chromium(0) (1) +5 (2)+6
(4) (116-benzene) tricarbonylchromium(0)
(3, + + ,4,+4
5. IUPAC name for complex [Mn(7t-C6H5) (CO)3]:
17. Coordination number of Cr is six. A complex with C202~,
( 1 ) Tricarbonyl (Ti 5-cyclopentadiene)manganese(I)
(2 ) Tricarbonyl (Ti 5 -cyclopentadi ene)manganate(I)
::r:%:€:;I:r(°exn£):e(8:):]8£L[belntheratiotomckecomp|ex
(3) Tricarbonyl (11 5-cyclopentadienyl)manganese(I)
XJ'Z
(4) (11 5-cyclopentadienyl) tricarbonyl manganese( 1 )
(1) 1 1 I
6. Ligand with two or more points of attachment to single
(2) 1 1 2
metal atoms are called:
(3) I 2 2
(1) Monodentate ligand (2) Chelating ligand
(4) 2 1 1
(3) Ambidentate ligand (4) None of these
18. The compound [CoC13I(C5H5N)2]Br will show the chemical
7. The number of ions produced by the complex
test for which of the following ions?
[CrovH3)4C12]C103 is
(1) Br° (2)C|°
(1) 2 (2)3
(3) 4 (4) 6 (3) 1© (4)Br© as well as c1©

8. Which of the following is a tridentate ligand? 19. The correct IUPAC name of [Mn3(CO)i2] is

(1) N02® (2)Oxalate ion (I)Dodecacarbonylmanganate(0)

(3) Glycinate ion (4) Dien (2) Dodecacarbonylmanganic(II)
 Coordination compounds 7.95

(3) Dodecacarbonyltrimanganese(0) (4) None of the above

(4) Manganiododecarbonyl(0) 28. Which of the following is nonionisable?
20. The correct name of (I) [coavH3)3ci3] (2) [cOovH3)4ci2]ci
(3) [CO(NH3)5Cl]C12 (4) [CO0VH3)6]C13
(CO)3F<:§>Fe(CO)3ls 29. Which of the following pair contains complex salt and
double salt respectively?
( 1 ) Tri-#-carbonylbis(tricarbonyl iron(0))
(1) Fes04, K4[Fe(CN)6]
(2) Hexacarbonyliron(Ill)pr-tricarbonylferrate(0 )
(2) [CuOVH3)4]S04, Fes04.7H20
(3 ) Tricarbonyl iron(0)pr -tric arbonyliron(0)
(3) [CuOVH3)4]S04, K2S04A12(S04)3.24H20
(4) Nonacarbonyl iron
21. The correct IUPAC name of the complex: (4) Mgs04.7H20, CuS04.5H20
OH 30. In which of the following compounds the metal is in the
I
lowest oxidation state?
(1) [Co0VH3)5Br]S04 (2) Fe3[Fe(CN)6]2
=::]=;}COC121S (3) [Mn2(CO)[o] (4) K[Ptc13(C2H4)]
OH 31. Which of the following can be termed as mixed complex?
(1)Dichloridodimethylglyoximatocobalt(II) (I) K4[Fe(CN)6] (2) [Cu(NH3)4]S04
(2) Bis(dimethylglyoxime) dichlorocobalt(II) (3) [coavH3)4No2cl]cl (4) K2Feso4
(3) Dimethylglyoximecobalt(II) chloride 32. The oxidation number of co in [Co(en)3]2(S04)3 is
(4) Dichloridodimethylglyoxime-N,N-cobalt(II) (I) +2 (2) +1
22. The correct IUPAC name. of [AIC13].4(EtoH) is (3) +3 (4) +6
( 1 ) Aluminium(II) chloride-4-ethanol 33. The IUPAC name for the coordination compound
(2) Tri chloridoaluminium(Ill) -4 -ethano I Na3[Ag(S203)2] is
(3 ) Aluminium(Ill) chloride-4 -hydroxyethane ( 1 ) Sodium silverthiosulphate(I)
(4) Aluminium chloride-4-ethanol (2) Sodium silverhyposulphate(I)
23. In octaamine-A-dihydroxodiiron(III) sulphate, the number (3) Sodium bis[argentothiosulphate(I)]
of bridging ligands is (4) Sodium bis(thiosulphato)argentite
(I)2 (2) 1 34. The IUPAC name for the coordination compound
(3) 3 (4) None [CuC12(CH3NH2)2] is
24. The IUPAC name of the complex having formula ( 1 ) Dimethylamine copper(II) chloride
[(CO)3Fe(CO)3Fe(CO)3] is (2) Bis(dimethylamine copper(II) chloride
(I)Monocarbonylferrate(0) (3) Dichloridobis(methylamine) copper(II)
(2 ) Tricarb onyliron( 0 )-#-tricarb onyliron(0) (4) Dichlorobis(diinethylamine) copper(II)
(3)Tri-#-carbonylbis-{tricarbonyliron(0)} 35. The IUPAC name for [Al(OH)(H20)5]2+ is
(4) Hexacarbonyl-#-tric arb onyl iron(Ill) ( 1 ) Pentahyroaluminium hydroxide
25. A group of atoms can function as a ligand only when (2) Aquometaaluminate ion
(1 ) It is a small molecule (3) Pentaaquaaluminate(Ill) hydroxide
(2) It is capable of acting as donor of electron pair (4) Pentaaquahydroxoaluminium(III)
(3) It is a negatively charged ion 36. The IUPAC name for [Pt(Br)(C1)(NH3)30J02)]Cl is
(4) It is a positively charged ion. ( I ) Triamminechloridobromidonitroplatinum(IV) chloride
26. Which ofthe following is most likely structure ofcrc13.6H20 (2 ) Triamminebromido chl oridonitroplatinum(IV) chloride
if 1/3 of total chlorine of the compound is precipitated by
(3 ) Triammirmitrochlorobromoplatinuin(IV) chloride
adding AgN03 to its aqueous solution?
(4) Triamminechloronitrobromoplatinurn(IV) chloride
(1) Crc13.6H20 (2) [Cr(H20)3C13] (H20)3
37. The oxidartion number of cr in [Cr(C6H6)2] is
(3) [Crc12(H20)4]Cl.2H20 (4) [Crcl.(H20)5]C12.H20
(1) 0 (2) +2
27. The coordination number of the central ion may be obtained
(3) +3 (4) +6
from
38. Which of the following has five donor (coordinating) sites?
(1) The number of ionic bonds formed with the surrounding
ions ( 1 ) Ethylenediaminetriacetate ion

(2)The number of coordinate bonds formed with the (2) Diethylene triamine
surrounding atoms (3) Ethylenediaminetetracetate ion
(3) The number of ions of opposite charge immediately (4) Triethylene tetramine.
surrounding the specific ion
7.96 Inorganic chemistry

39. Which of the following is not chelating agent? (1)1>11>111 (2)111>11>1

( I ) Thiosulphate (2) Oxalato (3)11>1>111 (4)11-1>111

(3) Glycinato (4) Ethylene diamine 49. Increasing order EAN of the metals in
40. The solution of AgBr in presence of large excess of NH3 I. INi(CN)4]2~ II. [Fe(CN)6]3-
contains mainly the cation. Ill. [Cu(CN)4]3-is
(I) NH4© (2, Ag© (1)1<11<111 (2)1<11-Ill
(3) [Ag(NH3)]® (4) [Ag(N113)2]© (3)1<111<11 (4)111<11<1
41. Which of the following species is not expected to be a 50. EAN of Na[Ptc13(t|2-C2H4)] is
ligand?
(I) 86 (2) 78
(1) fo (2) NH4© (3) 84 (4) 34
(3) NH2 -NH3© (4) CO 51. BAN of [Fe(n2-C5H5) (CO)2Cl]:
42. The number of donor sites in dimethyl glyoxime, glycinato, (1)36 (2) 35
diethylene triamine and EDTA are respectively: (3) 37 (4) 34
(1)2,2,3 and4 (2)2,2,3and6 52. Ivhich has maximum BAN of the underbold atoms?
(3)2,2,2and6 (4)2,3,3 and6 (Cr = 24, Co = 27, Fe = 26, Ni = 28)
43. Which of the following is a double salt? (I ) [Cr(EDTA)]° (2) [Co(en)3]3+
(I) Alum (2) Chrome alum (3 ) [Ni(CN)4]2- (4) [Fe(C204)3]3-
(3) Microcosmic salt (4) All of these 53. Give FAN value of Mg in [Mg(EDTA)]2-:
44. When potash alum is dissolved in water the total number of (1) 16 (2)20
ions produced is
(3) 22 (4) 18
(1) Four (2) Eight 54. EAN of cobalt is 36 in [CoOVH3)202(en)Br]. Thus, 02 is
(3) Ten (4) Thirty-two (1) dioxide (2) superoxide ion
45. Which of the following statements is correct with regard to
(3) peroxide ion (4) oxide
a complex ion?
55. BAN of Fe in [Fe(C204)3]3-is
(1) A complex ion consists of a central ion bonded to two or
(1) 27 (2) 24
more donor ions or molecules, usually does not dissociate
into simple ions or molecules even in a solution, and (3) 35 (4) 29
exhibits properties different from its constituent ions or [Link](CO)3Fe\-/Fe(CO)3is
molecules.
(2) The donor ions and molecules which coordinate with the (CO)3
central atom or ion in a complex are called ligands. (1) 34 (2)35
(3) The sum of the number of electrons present in the central (3) 36 (4) 37
metal ion or atom and those donated by the ligands 'is
called the effective atomic number of the central metal Isomerism
atom and this number is. usually the same as the atomic 57. [CoOVH3)6] [Cr(CN)6] and [CrorH3)6] [Co(CN)6] are
number of the next higher noble gas.
( I ) Linkage isomers (2) Ionisation isomers
(4) All of these (3) Coordination isomers (4) None of these
46. How many moles ofAgcl would be obtained, when 100 mL 58. The type of isomerism present in pentaammine nitro
of 0. I M Co(NH3)5C13 is treated with excess ofAgN03? chromium(Ill) perchlorate is
(1) 0.01 (2) 0.02 (1) Optical (2) Linkage
(3) 0.03 (4) None of these (3 ) Hydrate (4) Polymerisation
47. 0.001 mol of Cr(NH3)5(N03)(S04) was passed through 59. Which one of the following has the largest number of
a cation exchanger and the acid coming out of it required isomers?
20 mL of 0.1 M NaoH for neutralisation. Hence, the
(1) [Cr(en)2C12]® (2) [Cr(N113)5Cl]2+
complex is
(3) [RuOVH3)4C12]® (4) [Ir(PR3)2H(CO)]2+
(I) [CrovH3)5S04]N03 (2) [CrovH3)5N03]S04
60. [CrovH3)5N02]S04 and [CrovH3)50NO]S04 are related to
(3) [CrovH3)5] (S04) OJ03) (4) None of these each other as:

Effective Atomic Number (EAN) ( 1 ) Geometrical isomers (2) Linkage isomers

48. Among the following, select the order of decreasing EAN (3) Coordination isomers (4) Ionisation isomers
values 61. Which one of the following will be able to show geometrical
I. [Cr(CO)6] 11. [Cr(CO)6]°
isomerism if complexes are square planar?

Ill. ,Cr(CO,6,® (1) Ma4 (2) Ma3b

(3) Mabcd (4) [M(AA)2]
 Coordination compounds 7.97

62. The number of geometrical and optical isomers of 73. Which of the following will show optical isomerism?
[crovH3)3oro3)3] is (1) [zncl4]2- (2) [cuavH3)4]2+
(i)3 (2)2 (3) [Cr(C204)3]3- (4) [Co(CN)6]3-
(3) 0 (4) 4 74. In which of the following pairs both the complexes show
63. Both geometrical and optical isomerisms are shown by optical isomerism?

(1) [CO(en)212]® (2) [CoOVH3)21]2+ ( I ) Cis-[Cr(C204)2C12] 3-, Cis-[CO0VH3)4C12]

(3) [Cr(OX)3]3- (4) [CO0VH3)412]® (2) [CO(en)3]C13, Cia-[CO(en)2C12]Cl

64. In [Co(C204)3]3-, the isomerism shown is (3) [C00V03)30VH3)3] , Cis-[Pt(en)2C12]

(4) [Ptcl(en)C1] , INic12Br2]2-
(l) Ligand (2) Optical
75. Which of the following gives the maximum number of
(3) Geometrical (4) Ionisation isomers?
65. Which of the following octahedral complex does not show
(1) [CO0VH3)412] (2) INi(en)OVH3)4]2+
geometrical isomerism (A and 8 are monodentate ligands)?
(3) INi(C204)(en)2] (4) [Cr(SCN)20VH3)4]®
(I) [MA383] (2) [MA482] 76. The possible number of optical isomers in [Cr(en)2C12]© is
(3) [MA5B] (4) [MA284] (1)6 (2)3
66. FacialLmeridional isomers is associated with which one of (3) 4 (4) 2
the following complex? (M = central metal) 77. Which of the following does not have optical isomers?
(1) [M(AA)2] (2) [MA383] (1) [Co(en)3]Br3 (2) [CO0VH3)3Br3]
(3) [MABCD] (4) [M(AA)3] (3) [Co(en)2Br2]Br (4) [Co(en)OVH3)2Br2]Br
67. The total number of possible coordination isomer for the 78. Which of the following will give a pair of enantiomolphs?
given compound [Pt(NH3)4Br2] [PtBr4] is (1) [CrQVH3)6] [Co(CN)6] (2) [CO(en)2C12]C1
(1)2 (2)4 (3) [PtovH3)4] [Ptc16] (4) [C00VH3)4C12]N02
(3) 5 (4) 3 79. Both Cr3+ and Pt4+ have a coordination number of 6. Which
68. The following complexes are given of the following pairs of complexes will show approximately
the same electrical conductance for their 0.1 M aqueous
I. fra#S-[CO0VH3)412]® 2. C!.S-[COO{H3)2(en)2]3+
solutions?
3. fr¢#s-[Co0VH3)2(en)2]3+
(1) Crc13.4NH3 and Ptc14.4NH3
4. INil4]2-
(2) Crc13.3NH3 and Ptc14.5NH3
5. [TiF6]2-
(3) Crc13.6NH3 and Ptc14.5NH3
6. [CoF6,3-
(4) Crc13.5NH3 and Ptc14.6NH3
Choose the correct code. 80. Select the correct statement for [M(AB)b2cd]:
(1) 4, 5 are coloured; 6 is colourless (I) All geometrical isomers are optically active.
(2) 2 is optically active; 1, 3 are optically inactive (2). It has four trams isomer with respect to b.
(3) I, 2 are optically active; 3 optically inactive (3) It has seven geometrical isomers.
(4) 4 is coloured; 5, 6 are colourless (4) It has three cis and two trams isomers with respect to b.
69. The following represents a pair of enantiomers: 81. Which one of the following coordination compounds
exhibits ionisation isomerism?
( 1 ) fra#s-[Crl2en2]© (2) CZ.a-[Crl2en2]®
(1) [Cr(N113)6]C13 (2) [Cr(en)3C13]
(3) fra#s-[Crl20VH3)4]® (4)C!.a-[Crl2(N113)4]®
(3) [Cr(en)3]C13 (4) [CO(NH3)5Br]S04
70. The compound [PtBr2(NH3)2] can form
82. Which of the following complex compounds exhibits
( 1 ) Geometrical isomers (2) Coordination isomers cz.a-f7'¢#s isomerism?
(3) Optical isomers (4) Linkage isomers ( I) [Ptc12(N113)2] (2) [Pdc12Brl]
71. The compound [Crc12(NH3)2(en)] Can form (3) [Pto¢H3) ®y) (C1) (Br)] (4) All of these
( 1 ) Geometrical isomers (2) Coordination isomers 83. How many geometrical isomers are possible for the square

(3) Optical isomers (4) Linkage isomers planar complex [Ptov02)®y)OVH3)OVH20H)]N02?

(1) Four (2) Five
72. One mole of complex compound Cr(NH3)5C13 gives 3
moles of ions on dissolution in water. One mole of the same, (3) Eight (4) Three
complex reacts with two moles ofAgN03 to yield two moles 84. :cot:££edfra[ :temp:::,::n£:%o&#;;;c,:T®Tgements of the
of Agcl(s). The complex is
(1) [CrovH3)4C1]C12.NH3 (2) [CroJH3)4C12]Cl.NH3
(3) [CrovH3)5C1]C12 (4) [CrovH3)3C13].2NH3
7.98 Inorganic chemistry

=_ - __I
CI NH3
86. Which would exhibit coordination isomerism?
(1) [CrovH3)6] [Co(CN)6] (2) [Cr(en)2C12]®
(3) [CrovH3)6]C13 (4) [Cr(edta)r]
87. Ivhich would exhibit ionisation isomerism?
(1) [CO(NH3)6] [(C204)3] (2) [C0quH3)5Br]2+ SOS-
(3) K3 [Fe(CN)6] (4) K3 [Fe(C204)3]
88. The water-soluble complex among the following is
(I) INi(HDMG)2] (2) [CO0VH3)3C13].
(3) Ni(CO)4 (4) INi(IIDMG)2]C12
89. Arrange the following optical activity possible in
Which of the following statements is incorrect regarding
these structures?
(:) :::#?):&:32,,3:11,]©© (:) :::(:£)#!®
(I) I and 11 are enantiomers
90. When an excess of ammonia solution is added to CuS04
(2) 11 and Ill are cz.a and /rcz#s isomers respectively
which solution is fomied?
(3) Ill and IV are f7~cz#s and cz.a isomers respectively
(1) [Cu(N113)2]2+ (2) [Cu(N113)4]©
(4) 11 and IV have identical structures.
(3) [CuOJH3)2]® (4) [CuOJH3)4]2+
85. Which of the following pairs of structures represent facial
91. Copper sulphate solution reacts with KCN to give
and meridional isomers (geometrical isomers) respectively?
( 1) Cu(CN)2 (2) CuCN
CICl
(3) K2 [Cu(CN)4] (4) K3 [Cu(CN)4]
CI NH3 92. The ionisation isomer of [Co(H20)4Clo{02)]Cl is
(1) [CO(H20)40T02)]C12 (2) [CO(H20)4C12]N02
and
(3) [Co(H20)4Cl(ONO)]Cl (4) [CO(H20)4C120V02)].H20
93. The 0.0001 molal solution of a complex AB]o has the
freezing point of +).0015°C in water. Assuming 100%

::Stsh°ec[caot£:I:[Link]:oP[=X]'.£6ndkih:I)P]roperrepresentation
(1) [AB8] (2) [A83]87
(3) [A87] 83 (4) [A85] 85
94. From the information given in the passage, what is the most

:]#oC;f63fi_¥:t::;%fot&eoc2°):3£;td-electronsforthespecies
( 1) both (A) and (8) have low spin
(2) (A) has high spin; (8) has low spin
(3) (A) has low spin; (8) has high spin
(4) Both (A) and (8) have high spin
95. The hybridisation states of the central atom ion in the
complex ions [FeF6]3-, [Fe(H20)6]3+ and INioJH3)6]2+ are:

( I ) sp3d2, dy2 and c# respectively

(2) all 3d2 4s 4p3
NH3
(3) all 4s 4p3 4d2
(4) sp3d2, c7sp3 andp4d2 respectively
 Coordination compounds 7.99

96. Among (A) TiF2-, (8) CoF3-, (C) Cu2C12 and (D) Nic12- (I)sp3,ds2p,dsp2 (2:)sp3,dsp2,sp3
(atomic number of Ti = 22, Co = 27, Cu = 29, Ni = 28), the (?)dsp2,sp3,sp3 (4) sp3 , sp3 , dsp2
colourless species are: order of decreasing number of
[Link] the following in
(1) (B) and (D) (2) (A) and (B) unpaired electrons.
(3) (C) and (D) (4) (A) and (C) I. [Fe(H20)6]2+ 11. [Fe(CN)6]3-
97. The magnetic moment of a complex ion is 2.83 BM The Ill. [Fe(CN)6]4- 11. [Fe(H20)6]3+
complex ion is: (1') IV,I,11,Ill (2) I, 11, Ill, IV
(1) [Cr(H20)6]3+ (2) [Cu(CN)6]2- (3) Ill, 11, I, IV (4) 11, Ill, I, IV
(3) [V(H20)6]3+ (4) [Mnc14]2- 107. A substance which is not paramagnetic is
98. Which of the following statements is not true for the reaction (1) Cr(C104)3 (2) KMn04
given below? (3) Tic13 (4) VOBr2
[Cu(H20)6]2+ + 4NH3 ± [CuOVH3)4]2+ + 4H20 108. Which of the following statements is correct?
(1) It is a ligand-substitution reaction (I) INic14]2-complex is more stable than INi(ding)2] due to
higher CFSE value.
(2) NH3 is a relatively strong-field ligand while H20 is a
weak field ligand. (2) With d2sp3 hybridisation [Fecl(CN)4(02)]4- complex is
diamagnetic.
(3) During the reaction, there is a change in colour from light
blue to dark blue. (3) :¥{88}:][Link] not Very stable and easily reduces to

(4) [Cu(NH3)4]2+ has a tetrahedral structure, and is

(4) Ligands such as CO, CN©, NO© are IT electron donor due
paramagnetic.
to the presence of filled 7t-molecular orbital.
Hybridisation, Magnetic and Optical Properties [Link] aqueous solution of titanium bromide shows zero
99. The c7-electron configurations of Mn2+, Fe2+, Co3+ and Ni2+
magnetic moment. Assuming the complex as octahedral in
are 3d5, 3c¢, 3cf, 3d8, respectively. Which of the following
aqueous solution, the formula of the complex is
aqua complexes will exhibit the minimum paramagnetic (1) [TiBr6]3- (2) [Ti(H20)6]Br4
behaviour? (3) [TiBr6]2- (4) [Ti(H20)4 Br2]
(I) [Fe(H20)6]2+ (2) [Co(H20)6]3+ Ilo.8je.:8#]'2_h,y[bMrif:Sra4t]`2°_?aanndd[FeaFg]:££,Cre:;emc:i:te]°yf:Fee£°ns
(3) [Mn(H20)6]2+ (4) [Ni(H20)6]2+
100. Which of the following is paramagnetic? ( 1 ) Tetrahedral, square planar, octahedral:
dsp2,sp3,sp3di..O,5.9,4.9.
(1) [Fe(CO)5] (2) [Cr(CO)6]
(3) [Fe(CN)6]4- (4) [CrovH3)6]3+ (2) Tetrahedral, square planar, octahedral:
101. The pair in which both species have same magnetic moment sp3,dsp2,sp3d2..5.9,0.4.9.

(spin only value) is (3) Square planar, tetrahedral, octahedral:

dsp2,sp3,d2sp3..5.9,4.9,0
(1) I[Cr(H20)6]2+, [CoC14]2-
(2) [Cr(H20)6]2+, [Fe(H20)6]2+ (4) Square planar, tetrahedral, octahedral:
dsp2,sp3,sp3d2..0,5.9,4.9
(3) [Mn(H20)6]2+, [Cr(H20)6]2+
Ill. The correct order of magnetic moment (spin values in BM) is
(4) [CoC14]2-, [Fe(H20)6]2+
(Atomic number Mn = 25, Fe = 26, Co = 27)
102. Select the correct order of magnet'ic moment (in BM) from
I. [MnBr4]2-II. [Fe(CN)6]4-Ill. [CoBr4]2-
the following options :
(I)11>111>1 (2)1>11>111
I. [Mnc14]2-II. [CoC14]2-Ill. [Fe(CN)6]4-
(3)11>1>111 (4)1>111>11
(1)1>11>111 (2)111>11>1
112.A square planar complex is formed by hybridisation of
(3)111>1>11 (4)1>111>11
which atomic orbitals?
103. Which of the pair of complex compounds are tetrahedral as
(I) S, Px, Py, dyz (2.) S. Pxo pyo dx2_y2
well as diamagnetic?
(5) S,Py,Pz,dry (4) S,Px,Py,dz2
(1) [CoC14]° and [Co(CO)4]e
113. The colour of a complex compound is due to:
(2) [Ag(SCN
(1) Promotion of 3cJ-electrons of the central atom/ion to
}d2:nadn:N¥:C#::
(3) [Co(CO)4]° and [Ni(CN)4]4- 4p-orbitals
(4) [Pdc14]2~ and INi(CN)4]2-
(2) Promotion of 3d-electrons of the central atom/ion to
104. Which of the following has a square planar geometry? 4s-orbitals
(1) [Ptl4]2- (2) [Col4]2- (3) Promotion of 3d-electrons of the central atom/ion within
(3) [Fel4]2- (4) INil4]2- d-orbitals
105. Among INi(CO)4], INi(CN)4]2-and INiBr4]2-species, the (4) Promotion of 4s-electrons of the central atom/ion to
hybridisation state of Ni atoms are respectively: 4p-orbitals

L
[Link] Inorganic chemistry

114. If a transition-metal compound absorbs violet-indigo (1) SCN©< Fe < cN° (2) scNe < CNO < FO
radiation in the visible region. Its colour would be
(3) F°< scN° < cN© (4) F© < cNe < SCN©
(1) Green (2) Yellow 126. The increasing order of the crystal field splitting power of
(3) Orange (4) Blue some common ligands is
115. Transition metal compounds are usually coloured. This is
(1) NH3 < N02© < CN° < H20
due to the electronic transition:
(2)H20<N02°<CN°<NH3
(I) From cJ-orbital to s-orbital
(2) Fromp-orbital to s-orbital (3)H20<NH3<N02°<CN°
(3) From d-orbital to p-orbital (4)H20<NH3<CN°<N02°
(4) Within the d-orbitals 127. The value of "spin only" magnetic moment for one of the
116. Which of the following compound is not coloured? following configuration is 2.84 BM. The correct one is
(I ) Na2[CuC14] (2) Na2[Cdc14] (1) cr (in strong field ligand)
(3) K4[Fe(CN)6] (4) K3 [Fe(CN)6] (2) cZ (in weak field ligand)
117. The colour of Cu© compound is (3) d3 (in weak as well as in strong field ligand)
(1) White (2) Blue (4) d5 (in strong field ligand)
(3) Orange (4) Yellow 128. The complexion which has no d-electron in the central metal
atom is
Crystal Field Theory (CFT)
(1) [Mn04]° (2) [CoOJH3)6]3+
118. Which of the following complex has higher Ao value?
(3) [Fe(CN)6]3- (4) [Cr(H20)6]3+
(1) [Fe(H20)6]2+ (2) [Fe(H20)6]3+
129.¥i:he(°:ih)e5:°2]][°h:tTfgs:::::e:Et:]]:Sc:°o:::tc:°:t::r[Link];ex
(3) [Fe(CN)6]3- (4) All have equal
119. Relative to the average energy in the spherical crystal field,
the t2g orbitals in tetrahedral field is (I)d2sp3hybridisedanddiamagnetic
(2) sp3d2 hybridised and paramagnetic
(1) Raised by (2/5) At (2) Lowered by (2/5) At
(3) Raised by (3/5) At (4) Lowered by (1/5) At (3 ) sp3d2 hybridised and diamagnetic
120. The crystal field splitting energy for octahedral (Ao) and (4) c72sp3 hybridised and paranagnetic
tetrahedral (At) complexes is related as: 130. Which of the following complex is inner orbital as well as
low spin complex?
(1) At=;Ao (2)At= +Ao
(1) [Cr(H20)6]3+ (2) [Fe(CN)6]3~
(3) [Cu(CN)4]3- (4) [MnovH3)6]2+
(3) Ao= -2At (4)Ao = -£At
131. The magnetic moment of a certain complex (A) of Co was
121.[Cr(H20)6]C13 (atomic number of Cr = 24) has a magnetic found to be 4.89 BM and the EAN as 36. Co also forms
moment of 3 . 83 BM. The correct distribution of 3d-elections complex (8) with magnetic moment 3.87 BM and FAN
in the chromium present in the complex is as 37, and complex (C) with EAN as 36 but diamagnetic.
Which of the following statements is true regarding the
(I) 3d[jry, 3dLyz, 3dLar (2) 3d]ry, 3d)yz, 3d]z2
above observation?
(3) 3d[(x2_,2), 3d]z2, 3d[zx (4) 3d'ry, 3d`(,2_,2), 3d[xz
(l)The oxidation states of Co in (A), (8) and (C) are
[Link],themagnitude +3, +2 and +3, respectively.
of Ao [CFSE in octahedral field] will be maximuln? (2)::rep:ecx)efa(sAd)spa3nfy(bBri)dfhs:Yfeonsps:a?[Link]£Sationstate
(1) [Co(CN)6]3- (2) [CoF6]3-
(3) [CO0J02)6]3- (4) [Co0VH3)6]3+ (3) The spin multiplicities of Co in (A), (8) and (C) are
123. In which of the following configurations will there be the 3, 2 and 1, respectively.

possibility of both para and diamagnetism, depending on the (4)The oxidation states of Co in (A), (8) and (C) are
nature of the ligands? + 6, +8 and +1, respectively.

(I) dB (2:) dn [Link] only magnetic moments of a d8 ion in octahedral,

(3) d6 (4) d5 square planar, and tetrahedral complexes, respectively, are
[Link] Mn3+ ion, the electron pairing energy P is about (I)2.8BM,Oand2.8BM (2)0,OandoBM
(3) 2.8, 2.8 and 2.8 BM (4)None of these
i#(°€#3LiaAr:VLa5L,u8eosofi:rmt±ieacn°dm3P::5Xoe6[c::{¥:sop)e6j:i+v:y: 133. Given the following data about the absorption maxima of
which of the following complex is high spin: several complex ions, what is the order of Ao for these ions?
(I) Both are high spin (2) [Mn(H20)6]3+ C ompound ^max
(3) [Mn(CN)6]3- (4) None of these I. [Crc16]3- 758
125. Which of the following ligands are correctly represented in II. [Crqul3)6]3+ 465
an spectrochemical series? Ill. [Cr(H20)6]3+ 694
 Coordination compounds 7.101

( I) Ao (I) < Ao (11) < Ao (Ill) (2) It is a non-ionic complex.

(2) Ao (11) < Ao (Ill) < Ao (I) (3) It is a tetrahedral complex.

(3) Ao (I) < Ao (Ill) < Ao (11)

(4) It is very effective for selective hydrogenation of organic
molecule at room temperature and pressure.
(4) Ao (Ill) < Ao (11) < Ao (I)
144. Which bond properties are consistent with one another?
134. Predict the order of Ao for the following compounds:
Bond order Bond length Vibrational frequency
I. [Fe(H20)6]2+ II. [Fe(CN)2(H20)4]
( l ) higher shorter higher
Ill. [Fe(CN)4(H20)2]2-
(2) lower shorter lower
(1) Ao(I) < Ao(II) < Ao(III) (2)Ao(II) < Ao(I) < Ao(Ill) (3) higher longer lower
(3) Ao(Ill) < Ao(II) < Ao(I) (4)Ao(II) < Ao(Ill) < Ao(I) (4) lower longer higher
135. Among the following pairs of complexes, in which case the 145. Select the correct order of C-O bond order in mixed
Ao value is higher for the second compound.
phosphine carbonyl complex:
(I) [CO (H20)6]3+, [Rh (H20)6]3+ I. [MO(Ph3P)3(CO)3] 11. [MO(Ph2Pcl)3(CO)3]
(2) [C0 qul3)6]3+, [CoC16]3- Ill. [Mo(Phc12)3 (CO)3]
(3) [CO (H20)6]3+, [Co (H20)6]2+ (1)1>11>111 (2)1<11<111

(4) [cO (cN)6]3-, [cOoun3)6]3+ (3)I-11>111 (4)1<11>111

[Link] of the following c6mplexes have high. stability 146. Compare C-C bond length (x) of C2H4 in Zeise's salt and
constant (frf) value. Cl bond length 0;) of C2(CN)4 in K [Ptc13C2(CN)4]:

(I) [Pt Br4]3- (2) [Pt QUH3)Br3]e (1)jr =J, (2)J, =X

(3) j¥ = )/ (4) None of these
(3) [Pt ovH3)3Br]® (4) [Pt (NH3)4]2+
[Link] of the following organometallic compound is a
137. The complex ion having minimum wavelength of absorption
a and 7t-bonded?
in the visible region is:
( 1 ) [Fe(T|5i=5H5)2] (2) K[Ptc13(T|2i2H4)]
(1) Cis-[Cr Br2 (NH3)4]® (2) Trans-[CrBr2 0{H3)4]®
(3) [Co(CO)5 NH3]2+ (4) [Fe(CH3)3]
(3) [Cr o¢H3)6]3+ (4) [Cr Br (NH3)5]2+ 148. Which of the following statement(s) is/are true or false?
138. Select the pairs having green and violet colour respectively. S]: Complexes having cP or d]° configuration of metal ions
(1) (I) [Cr(H20)6]Br3; (II) [Cr(H20)4Br2]Br. 2H20 are always diamagnetic.
(2) (I) [Cr(H20)6]Br2; (II) [Cr(H20)6]Br3 S2: In organometallic compounds, carbon is bonded to
metals directly.
(3) (I) [Cr(ONO)(H20)5]Br2 (11) [CrQV02)(H20)]C12
S3: In Fe(CO)5, the Fe-C bond possesses both a and 7[
(4) (I) [Pr cl ovH3)3]N02; (II) [Pt ov02)OVH3)3]Cl
characteristics.
139. Select incorrect match between compound and reason for its
observed colour. S4:Extrastabilityofmetalcarbonylsisexplainedbysynergic
bonding.
(I) H812: Polarization
(1) TTTT (2) FTFT
(2) A82P04: Polarization
(3) TTFF (4) FTTT
(3) [Fe(H20)5NO]S04: d-d transition
149. Which of the following complex can act as an oxidising
(4) Mn04©: charge transfer spectrum. agent as well as reducing agent?
140.:fhtahtewco°u]L°durbe°tfheINCL:(1:i?:2(#(2e]:;3](2[+)(i)S)):Lue-Puxplethen (1) Mn(CO)5 (2) Ti(CO)6
(3) Mn(CO)6 (4) None of these
(1) Violet (2) Deep blue 150. Which of the following statements is correct for the
(3) Pale blue (4) Green [Fe(H20)5NO] S04 Complex?
[Link] is the following compounds absorbs at shorter (1) The BAN value of Fe in this complex depends on the
wavelength in visible spectrum? charge of NO ligand.
(I) [Cr Br3 (H20)3].3H20 (2) [Cr Br2(H20)4]Br.2H20 (2) The EAN value of Fe in this complex does not depend on
(3) [Cr Br (H20)5]Br2.H20 (4) [Cr (H20)6]Br3. the charge of NO ligand.
142. CFSE value for brown ring complex for test of N03© ion is (3) The hybridisation of the central atom is #sp3.
(1)-2.4 Ao (2)-I.8 Ao (4) It is paramagnetic with / = I.73 BM
(3) |].8 AO (4) ro.4 AO [Link]
compound?
Application of Coordination Compounds and Miscellaneous
( l ) Ferrocene (2) Cis-platin
143. Which of the following is incorrect about Wilkinson's
(3) Zeise's salt (4) Grignard reagent
catalyst?
[Link] the following, which is not the 7t-bonded
(I) It is a diamagnetic complex. 6rganometallic compound?
7.102 Inorganic chemistry

(1) (CH3)4Pb (2) [Cr(T|6-C6H6)2] 163. The most stable ion is

(3) [Fe(n5-C5H5)2] (4) K[Ptc13(112-C2H4)] (1) [Fe(C204)3]3- (2) [Fe(Cl)6]3-

[Link] is an important component of which biomolecule (3) [Fe(H20)6]3+ (4) [Fe(SCN)6]3-
occurring extensively in living world? 164. The number of a and 7[-bonds in Fe2(CO)9, respectively, are
( 1 ) Haemoglobin (2) Chlorophyll (1) 22o and l57t (2) 22o and l67t
(3) Florigen (4) ATP (3) 23o and l57t (4) 15o and 87[
[Link] is the shape of Fe(CO)5 molecule and which of the 165.£[8A©g{°c¥)S2T©:n[yAcg°(g2P::%S._:°meoftheseare[Agqul3)2]©,
following cJ-orbitals involved in hybridization?
(I)Tetrahedraldx2_,2 Which of the following statements i`s true?
(2) Trigonal bipyramidal, dx2_,2 (1) In these complexes, Ag© is a Lewis base
(3) Trigonal bipyramidal, dz2 (2) The hybridisation of Ag© is sp2.
(4) Square pyramidal 4 (3) The Ag© complexes are good reducing agents
][Link]°p::xft£:,tEre°:eetrioff;r;;e)It::sd::;nab(;t#o£:£tnog;a(r€! (4) These complexes are all linear
166. Hardness of water is estimated by simple complex formation
metal species is titration. Complex formed by cation in hard water during
(I)B, C (2)A, B, C estimation of hardness is
(3) C,A (4)A, B (1)Na2[Ca(P03)6] (2) Na2[Mg(EDTA)]
156. Ferrocene is (3) [Ca(S04)2]2- (4) Na2[Pb(EDTA)]
( 1 ) [Fe(n2i6H5)2] (2) [Fe(T`5i5H5)2] 167. The ligand called 7t-acid is
(3) [Fe(T|6i6H6)2] (4) [Fe(T`3i=3H3)2] (I) CO (2) C2042-
157. Dimethylglyoxime is coordinated to Ni2+ through: (3) NH3 (4) ethylene
(1) Two oxygen atoms 168. The complex used as an anticancer agent is
(2) Two nitrogen atoms ( i ) mer-[C00VH3)3C13] (2) Cis-[Ptc12quH3)2]
(3) Two oxygen and one nitrogen atoms (3) Na2[CoC14] (4) Cis'K2[Pt(C12Br2)]
(4) Two oxygen and two nitrogen atoms 169. Which is uses in cancer chemotherapy?
158. In isolated condition C{ bond length of C2H4 is x, than the (I) cis-platin (2) Zeisse's salt
bond length ofn C-C bond of c2H4 in Zeise's salt is (3) Both (1) and (2) (4) None of these
(I) Greater than x (2) Less than x 170. Zeise's salt is
(3) Equal to x (4) None of these ( I ) Cr(i|6{6H6)2
159. When K4[Fe(CN)6] is treated with Fec13, a blue colour is
(2) Fe(n5c5H5)2
obtained. It is due to the formation of
(3) K[pt(n2iJ2H4)cl3]
(I ) Fell [Fe][[(CN)6]® (2) Fe[][ [Fe]](CN)6]°
(4)K[Pt(t|2{2H4)2C12]
(3) Both (1) and (2) (4) None of these |7|.[¥g=?::jchlorldoplatlnum(II),[Ptou3)2C12],1S
160. The common features among the species CN°, CO and
No© are
(1) bond order three and isoelectronic
(2) bond order three and weak field ligands
One of the number of platinum coordination compound
(3) isoelectronic and weak field ligands
is used in the treatment of cancer. Commonly known as
(4) bond order two and 7t-acceptors cis-platin, this compound has the ability to block the
161. Consider the following complex: uncontrolled division of cancerous cells that results in the
[Coqu3)5C03]Bro growth of tumours. Recent studies show that cisplatin can
the coordination number, oxidation number, number of cause serious side effects, including severe kidney damage.
d-electrons and number of unpaired d-electrons of the metal cis-platin is replaced by which of the following compounds:
are respectively: 2+

(I)6,3,6,0
(3)7,2,7,I
(2)7,1,6,4
(4)6,2,7,3
[Link] bond length of CcO bond in carbon monoxide is
1.128A. The C-O bond in [Fe(CO)5] is
in
ii:)Pt<:(CH2)„-:23#)Pt<:3I
trans-isomer(n = 2 to 6)

(1) 1.115A (2) I.128A

(2)
(3) I.178A (4) 1.150A
E¥)Pt<:2(cH2)„_H2:L>Pt<N:I
(n - 2 to 6)
 Coordination compounds 7.103

(I) 1' 11 (2)I,11,Ill

(3)[:;¥>Pt<;:2(cH2)„_::#>Pt<NC:I (3) 11,Ill (4) I, Ill, IV

181. Slow spin octahedral complexes show strong distortion.

(I) ,2g e8 (II) ,2g eg

(4) None of the above is correct.
172. Select the incorrect statement about metal carbonyls? (Ill) ,gg c: (IV) ,gg e:
(1) Metal acts as Lewis base as well as Lewis acid (I) I,11 (2) I, 11, Ill
(2) CO acts as Lewis base as well as Lewis acid (3) Ill, IV (4) I, Ill, IV
(3) p7t-p7t back bonding takes place 182. Which of the following configuration in either high spin or
(4) p7t-c77t back bonding takes place low spin complexes show no distortion.
173. The following metal carbonyls are given:
(I) ,2g e3 (II) ,gg e3
(I, ,Mn(CO,6]©
(11) [Cr (CO)6] (Ill) ,2g e8 (IV) ,!g ei
(Ill, [V(CO,6]O
(1) I,11 (2) 11, Ill
Which of the following is correct order of CO bond strength
(3) I, 11, Ill (4) All
in the above complexes
183. Which of the following statement is/are correct.
(I)1>11>111 (2)111>11>1
(I) Cr has greater trams effect than NH3.
(3)11>1>111 (4)111>1>11
([])iF::nesr)egne:tit:Str:Snesd]s]:i::sst=tfhnegsffsro°£Cpits€::£i?n(cis-
174. The following compounds are given:
(I) [Mn(CO)]° (II) CO
(Ill) Starting from [PtovH3)4]2+, the synthesis of cisplatin
(Ill) Oc i BH3 (IV) [Fe(CO)5] (cis-isomer) is obtained exclusively.
Select the correct CO bond order in the given compounds
(IV) CH3- has greater trams effect than H-.
(1)IV>III>I>II (2)I>IV>III>II (I) 1' 11 (2) 11,Ill
(3)II>I>IV>III (4)III>II>IV>I (3) Ill, IV (4) I,Ill
175. The 7t-acid ligand which uses its c7-orbital during synergic
bonding is its complex compound is:
(1) PR3 (2) CO
(3) C6H6 (4) NO© Naming, Terminology and Ligands
176. Which of the following ligand does not act as 7t-acid ligand? 1. Select the correct statement(s) for double salt.
(I) 022- (2) C2H4 ( I ) Double salts are stable in solid state but lose their identity
(3) N2 (4) CO in aqueous solution.
177. Select the correct statement about the above given compound (2) In double salt the properties of constituent ions are not
changed in their aqueous solution.
(1) `CcO' bond is weakest in cation and strongest in anion.
(2) `CcO' bond is strongest in cation and weakest in anion. (3) Double salts are stable in solid state and do not lose their
identity in aqueous solution.
(3) `CcO' bond is longer in cation than in the anion.
(4) In double salt the properties of constituent ions are
(4) (`M|') 7t-bonding is higher in the cation
changed in their aqueous solution.
178. The 7[-acid ligand which uses its d-orbital during synergic
2. Which of the following ligand(s) is/are ambidentate?
bonding in its complex compound.
(I) Nose (2) scNe
(1) NO (2) N2
(3) N09 (4) CH3COO©
(3) PR3 (4) CN°
3. Select the correct IUPAC name for [COC12(en)2]2(C103)2.
Jahn-Teller Distortion
( 1 ) Dichloridobis (ethylenediamine)cobalt(Ill) chlorate
179. Which of the following configuration is more stable for the
(2) Dichloridobis (ethane-1, 2-diamine)cobalt(III) chlorate
[CuOJH3)4]2+.
(3) bis {dichloridoethylenediaminecobalt(Ill)} chlorate
(1) /£g(dz2)2(dx2_y2)) (2) /£g(dz2)I(dx2_y2)2 (4) bis {di(chlorido)ethylenediaminecobalt(III) } chlorate
4. Bidentate ligands are
(3) ffg(dz2)2(dx2_y2)2 (4)All
(I) C2042-(oxalate)
180. Which of the following configuration high spin octahedral (2) en (ethylenediamine)
complexes shown strong distortion. (3) DMG (dimethyl glyoxime)
(I) ,2g ci (II) ,2g e3 (4) Gly (glycine)
5. Which of the following complex(s) is/are having correct
(Ill) ,2g e8 (IV) ,ig eg name?
7.104 Inorganic chemistry

( 1 ) CS[Pt(NH3)15] Ceasium amminepentaiodidoplatinate(IV) 14. Which of the following represent the correct sequence of
indic ated prop erty?
(2) [Ag(CN)2]° Dicyanidoargentate(I) ion
(3) Rb3[Cr(C204)3]-Rubidium trioxalatochromate(Ill) (1) Mn2+ < Ni2+ < Co2+ < Fe2+: magnetic moment

(4) K2INi(EDTA)] Potassium ethylenediaminetetraacetatoni (2) Feo > Coo > Nio: basic character
ckel(II) (3) Sc <Ti < Cr < Mn: number of oxidation states
6. Which can fomi chelates? (4) 1.73 #: one unpaired electron
( I ) Ethylene diamine (2) Oxalate 15. Which of the following complexes are diamagnetic?
(3) Glycinate (4) Cyanide
(I ) [Aul4]° (2) [Co(H20)6]3+
7[:1::;4t:eoi:i:SP:::aH:;4]fi?Tthef°]L°W]n8
(3) [Col6]3- (4) [CO(CO)4]©
16. Which of the following molecule(s) is/are showing optical
isomerism?

( 1 ) [CO0VH3)3Br3] (2) [CO(en)Br2(NH3)2]®

(1) Tetramminecobalt (Ill)-#-amido-#-peroxidotetraamm
inedicobalt (Ill) ion (3) [Co(en)3]3+ (4) [Co(en)2Br2]®

(2 ) # -Amido-A-peroxidobis (tetraammine) dicobalt-(Ill) ion 17. Both geometrical and optical isomerisms are not shown by
(3) #-Amido-#-peroxidobis(tetraamminecobalt(Ill)) ion ( 1 ) dibromidobis (ethylenediamine) cobalt(Ill) ion
(4) #-Amido-#-p eroxidooctaamminedicobalt(Ill) ion (2) tetraamminedibromido cobalt(Ill) ion
8. Which of the following statement(s) is/are correct? (3) tetraamminedibromido cobalt(Ill) ion
(1) Primary valency of the central metal of a complex is (4) trioxalatochromate(III) ion
always satisfied by anions.
18. Which of the following statement(s) is/are correct?
(2) Secondary valency of the central metal of a complex may
be satisfied by either negative ions or neutral molecules. (1) The complexes INil4]2-and INi(CN)4]2-differ in state of
hybridisation of nickel.
(3) Species which show primary valencies in a complex
compound cia be precipitated out. (2)The complexes [Nil4]2- and INi(CN)4]2- differ in
geometry.
(4) None of these
9. Which of the following complex(s) is/are an example of (3) The complexes INil4]2- and INi(CN)4]2- differ in the
magnetic properties.
homoleptic complex?
( 1 ) [CoO¢H3)6]3+ (2) [Cr(H20)6]3+
(4)Thecomplexes[Nil4]2-and[Ni(CN)4]2-differinprimary
valencies of nickel.
(3) INi(N113)6]2+ (4) INiovH3)4C12]
19. In which case geometrical isomer cis is possible with
10. Which of the following ligand(s) can act as 7t-acid ligand?
M as metal ion if complexes are square planar having
( 1 ) 83N3H6 (2) 7t-cyclopentadienyl CIN - 4?
(3) 7[-Allyl (4) a-cyclopentadienyl
(I) MX2Y2 (2) MX2YZ
Isomerism (3) MXY2Z (4) MX4
11. Which of the following molecule(s) is/are not showing 20. ##d]::t:;t:I? is involved in which of the following
optical isomerism?
( I ) [C00JH3)3l]® (2) [Co(en)(N113)2]2+ (I) sp3 dB (2:) dsp2
(3) [Co(H20)4(en)]3+ (4) [Co(en)20VH3)2]3+ (5) sp3 d (4) spa d
12. Which of the following complex ion(s) is/are not expected 21. Which complex species does/do not exhibit geometrical
to absorb visible light? isomerism and only have two stereoisomerism?
( I ) [Ti(en)20JH3)2]4+ (2) [CrovH3)6]3+ ( 1 ) [PtBrl(gly)]° (2) [Cr(EDTA)]°
(3) [ZnovH3)6]2+ (4) [SC(H20)30VH3)3]3+ (3) [Cr(acac)2(en)]® (4) [Pd(CN)(OX)(gly)]
13. The complex [Fe(H20)5NO]2+ is fomed in the brown ring 22. Which of the following complex(s) cannot exhibit both
test for nitrates when freshly prepared Fes04 solution is geometrical and optical isomerism?
added to aqueous solution of N03©followed by addition of (I) [CO(H20)Br3] (2) [Pt Br c| F|]-2
cone. H2S04. Select correct statements about this complex:
(3) [Fe c12 (en)2]® (4) [Ru(en)3]+3
(I) Colour change is due to charge transfer. 23. Select the correct statement about the complex
(2) It has iron in +1 oxidation state and nitrosyl as NO®. [CrBr(CN)(en)2]©?
(3) It has magnetic moment of 3.87 BM confiming three (1) It has three optically active isomers: cZ, / and frarus form
unpaired electrons in Fe.
(2) Only the cz.a isomer shows optical activity
(4) In complex Fe has d2sp3 hybridisation. (3) It shows two geometrical isomers cz.a and Jrtz#f .
(4) a.s and frcz#F forms are not diastereomers to each other
 Coordination compounds 7.105

24. Which of the following statement(s) is/are correct? ( I) Element always forms colourless coinpound.
(1) IUPAC name of Ca[Cr(CN)202(02)(H20)] is Calcium (2) Number of electrons in t2g orbitals are higher than in eg
aquedicyanoperoxosuper oxo chromate (Ill) orbitals.
(2) [Cr CI I (en)2]© shows optical isomerism (3) It can have either d3 or d8 configuration.
(3) [Pt abcd]"± type and [Pt abcedf]"± type compounds shows (4) It gan have either d7 or d8 configuration.
3 geometrical and 30 stereoisomer's respectively 33. Which of the following is/are characteristic of a tetrahedral
•(4) Cis and trams forms are diastereomers to each other complex?
25.[{;::Cr:(°of±h):&i!:)T!Piosnt;tementiscoITectforthecomplex (1 ) dx2_),2 and dz2 orbitals are low energy orbitals.
(2) Most tetrahedral complexes are high spin.
(1) It has three geometrical isomers (3) Crystal field splitting is found double in octahedral
(2) It shows four stereoisomer's complexes.
(3) Only one stereoisomer is optically active and remaining (4) Splitting pattern in tetrahedral complex is just opposite of
are inactive that in octahedral complexes.
(4) The complex have three unpaired e"s 34. The complex K4[Zn(CN)4(02)2] is oxidised into
26. In the test for N03° ion, the dark brown ring complex is K2[Zn(CN)4(02)2], then which of the following is/are
formed, which statement(s) is/are correct of this complex. cOITect:

( 1) Fe and No both have +1 charge (1) Zn(II) is oxidised in to Zn(IV)

(2) The colour is due to charge transfer spectra. (2) Paramagnetic moment decreases
(3) Fe has +2 oxidation state and NO is neutral (3) 0-0 bond length decreases
+1

(4) The complex can be represented as [Fe (H20)4NO]+2 (4) Paramagnetic moment increases
27. In in aqueous solution of NiBr2, if (e#) is progressively 35. Select the correct statement:
added in molar ratios such as Ni : en :: 1:1,1:2,I:3 then (1) [Co(H20)6]3+ is Co(Ill), low spin, 0 unpaired electron,
three octahedron complexes x, j/, z formed respectively. diamagnetic
Select the correct statement(s) about :¥, }J and z. (2) [CoF6]3- is Co(III), high spin d6, 4 unpaired electron,
( 1 ) Complex x has maximum value of absorbed wavelength paramagnetic
(2) Complex )/ is coloured (3) [RhF6]3- is Rh(Ill), low spin cf, 0 unpaired electrons
diamagnetic
(3) Complex z has maximum number of chelates
(4) All three are paramagnetic outer orbital complexes (4)[Fe(CN)6]4-is high spin d6, 0 unpaired electron
diamagnetic
28. Which of the following pair of complex compound(s) has/
have different colour? 36. [Co(H20)6]3+ complex is

(1) cJ and / form of INi(e#)3]2+ (1) High spin complex

(2) cis and trams form of [Irc12(e#)2]Br (2) Having d2sp3-hybridization
(3) [Cro+02)2(N113)4]© and [Cr(ONO)20VH3)4]® (3) Low spin complex
` (4) [CrcloJ02)0{H3)4]Cl and [Crc120VH3)4]N02
(4) Having octahedral structure
29. The complex INi(Pph3)2(CNS)2] is paramagnetic. The
37. Colourless, tetrahedral complexes among the following are

:#:£:°buyspcd°+¥:Joe:p°L:xP:s+/2arL::[Link] ( 1 ) K3 [Cu(CN)4] (2) CaINic14]

( i ) Polymerisation (2) Linkage (3) Na[BF4] (4) Ni(CO)4

(3) Optical (4) Geometrical 38. In which of the following complex ion five atoms are lying
30. Which of the following complex ion(s)/compounds shows in a line including metal?

geometrical isomerism but none of them shows optical (1) [Ag(CN)2]° (2) [Pt(CN)4]2-
isomerism?
(3) [Ag(SCN)2]° (4) [Zn(CN)4]2~
( I) [CoC14(e#)]° (2) [Pt Br I(H20)OVH3)] 39. Select the correct statement(s) for given carbonyl
(3) [Cr(en)3]3+ (4) [Crc13(H20)20VH3)] compounds:
31. In which of the following comp`ounds c7-orbitals lose their
(I) "CO" bond order is lesser in [Nb(CO)6]°
degeneracy?
Then in [Tc(CO)6]©
(1)AnhydrousCuS04 (2) K3[Fe(CN)6]
(2)«`:=9';obn°dn:rd°errdLenr[inc(tNob)(6:©°)6]°1Soreaterthan
(3) K4[Fe(CN)6] (4) CuS04.5H20

Hybridisation, VBT, CFT (3) [Tc(CO)6]© acts as reducing agent and INb(CO)6]° acts
32. A c7-block element forms octahedral complex, but its spin as oxidising agent.
magnetic moment remains same either in strong field or in (4) [Nb(CO)6]° acts as reducing agent and [Tc(CO)6]© acts
weak field ligand. Which of the following is /are correct? as oxidising agent.
7.106 Inorganic chemistry

40. Select the correct statement(s): (3) In an octahedral field, the t2g orbitals are raised in energy
(1) In c7sp2 hybridisation, dz2 orbital of central metal atom/ by 0.4Ao.
ion is used. (4) Stability of complex is:
(2) Facial and meridional isomers associated with [Ma3b3]"± INi (en)2]2+ > [Ni (DMG)2]
type complex compounds, both are optically inactive.
Application of Coordination Compounds
(3) In metal carbonyl CcO increases compared to that CO
molecule. 47. The coordination number of a central metal atom in a
complex(s) is/are not determined by:
(4) Chelation effect is maximum for five and six membered
rings. (1) The number of only anionic ligands bonded to the metal
ion.
41. Select the correct statements:
(1) Compounds [Cr(H20)6]Br3 and [CrBr3(H20)3].3H20 are
(2) The number of ligands around metal ion bonded by
7t-bonds.
hydrate isomers.
(2) Greater the charge on the central metal cation, greater the (3) The number of ligands around a metal ion bonded by
both 7t and a-bonds.
value of A(CFSE)
(3) [CrBr2(NH3)2(e#)]© complex ion will have four different
(4) The number of ligands around a metal ion bonded by
isomers.
a-bonds.
48. Which of the following statement(s) is/are incorrect?
(4) In the complex ion [CoF6]3-, F° is a weak ligand, so that
Ao < P and it is low spin complex. (I) Metal carbonyls are the examples of only a-bonded
42. Select the correct statement(s): organometallic complexes.
(2) Metal carbonyls are the examples of only 7[-bonded
(I) Ni(CO)4 is low spin complex
organometallic complexes.
(2) [FeF6]3-is high spin complex
(3) Metal carbonyls are the examples of organometallic
(3) Strong ligand like CN° and N02® generally form low complexes which involve both a and 7t-bonds between
spin complexes.
metal and carbon of the carbonyl group.
(4) Weak ligands F©, C1° and OHO usually form high spin
complexes. (4) Metal carbonyls involve both a- and 7t-bonds between
metal and oxygen of the carbonyl group.
43. Select the correct statement(s): for octahedral complexes:
49. Which of the following is an example of 7t-bonded
(1) In octahedral complexes, its magnetic moment remains organometallic complex?
same either in strong field or in weak field ligand in d9
configuration. . (1) Ferrocene (2) Dibenzenechromium
(3 ) Zn(C2H5)2 (4) Pb(C2H5)4
(2)Numberofe-'sint2gorbitalsarehigherthaninegorbitals.
(3) d3 and d8 configuration cannot exist in both high spin and 50. Which of the following is/are example(s) of a-bonded
low spin forms. organometallic compound?
(4) Chelating ligands are at least bidentate ligands. (I ) A12(CH3)6 (2) Pb(CH3)4
44. Select the correct stability order for the following complexes. (3 ) Zn(C2H5)2 (4) Ferrocene
(I) [Cu (trien)]2+ > [Cu (en)2]2+ > [Cu OVH3)4]2+ 51. Which of the following statement is correct regarding metal
(2) [Ir (H20)6]3+ > [Rh (H20)6]3+ > [Co (H20)6]3+ carbonyl?

(3) [Cr OVH3)6]3+ > [Cr OVH3)6]2+ > [Cr OVH3)6]© (1) In Mn2(CO)[o, bond order of Mn-Mn is 0.
(4) [Fe OVH3)6]3+ > [Fe OJ02)6]3-> [Fe (H20)6]3+ (2) In Fe2(CO)9, number of Fe-Fe bonds is I.
45. Select the correct statement(s): (3) In Ni(CO)4, all ,bond length are same.
(1) Order of energies of d-orbitals of metal ion in a square (4) Fe(CO)5 is diamagnetic.
planar complex is: 52. Select correct statements:
dx2 -y2 > dny> d: = dex= dyz
( 1) [Ni(en)3]2+ is less stchle than [NiovH3)6]2+.
(2) The CFSE of [CoOVH3)6]Br3 is -2.4Ao.
(2) Increase in stability of the complexes due to the presence
(3) The magnitude of CFSE in octahedral field depends on of multidentate cyclic ligand is called macro-cyclic
nature of the ligand.
effect.
(4) When NH3 is added to [Ni(H20)6]2+, its magnetic
moment does not charge. (3) [Ni(en)3]2+ is more stable than INiovH3)6]2+.

46. Select the correct statement(s) (4) For a given ion and ligand, the greater the charge on the
• metal ion, the greater is the stability.
(1) Stability order of complexes is
53. In which of the following cases, the synergic bonding takes
[Cr(OX)3]3-> [Cr(H20)6]3+ > [Co(ONO)6]3-> [CoF6]3-
place at the 7t-orbital of the ligand?
(2) Among cr, d5,' cf and d7 configuration for an octahedral
(I) [Ptc13(C2H4)]° (2) INi(PF3)4]
;°]Thp;;Xceos#aT]::[Link] CFSE ls given by low spin (3) Cr(C6H6)2] (4) [Fe(7t-C5H5)2]
 Coordination compounds 7.107

54. Which of the following statement(s) is/are correct? Paragraph 2

(1):#cS::±£!Lgi6:g+:Stantof[CO(H20)6]3+islargerthanthat Ligands are broadly classified into two types, classical and non-
classical ligands depending on their donor and acceptor ability.
(2) The cyano complexes are more stable than those fomed Classical ligands form classical complexes while non-classical
by halide ions. ligands forln non-classical complexes. Bonding mechanism in
non-classical is called synergic bonding.
(3) The stability of halide complexes follows the order
|0 > Bre > ci© > F°. 5. In compound [M(Co)„]Z, the correct match for highest
`M-C' bond length for given M, # and z respectively.
(4)Thestabilityconstantof[CuOVH3)4]2+islessthanthatof
[CuC14]2-.
M„z
(1) Ti 6 -2
(2) Mn 6 +1
(3) Cr 6 0

Paragraph 1 (4) V 6 -1
Consider the following isomers of [Co(NH3)2Br4]° and answer 6. Synergic bonding is absent in:
thequestL|n:ife=3 ( 1 ) INi(CN)4]4- (2) [Cr(CO)3(83N3H6)]

(3) [Mo(Co)6] (4) [Sc(Co)6]3+

7. Which is not 7t-acceptor ligand?
a
(1)OL{5H5

:3rNd;N:: (2) PH3

Br
(3)V
9
(8) (4) 83N3H6

Paragraph 3
Bond lengths and vibrational spectra are the two important
physical evidences supporting the. synergic bonding in non-
classical complexes. Vibrational spectra is based on the fact that

B:ri:rBr thecompressionandextensio;ofabondmaybeanalogoustothe
behaviour of a spring and obeys Hook's law:
NH3 8. In [Mn2(CO),o] carbonyl complex, which d-orbitals of
(C) Mn-atom is not involved in synergic bonding between Mn
and CO ligand.

1. Select the correct statement: (1) CJxp (2) dyz

(3) cZz* (4) None of these.

(1) Pairs of A and D are same and pairs of 8 and C are also
Same. 9. In which of the following complex stretching frequency
for CO ligand is least and bond energy of `M -C' bond is
(2) All have chiral centres.
highest.
(3) A and C are enantiomers.
(1) [MO(CO)3 (PR3)3] (2) [Mo(CO)3 (dien)]
(4) 8 and D are enantiomers.
(3) [MO(CO)3(PF3)3] (4) [MO(CO)3 (PC13)3]
2. Out of these isomers:
10. In which of the following ligand, a-bond strength does
(I) A and D are trams and 8 and C are cis
not change during synergic bonding in their respective
(2) A and D are cis and 8 and C are trams complexes.
(3) A and 8 are cis and C and D are trans
(1) P(C2H5)3 (2) N2
(4) A and 8 are trans and C and D are cis
(3) CH2 = CH2 (4) CO
3. In the complex [Zn PQRS]2+:
(1) There is chirality Paragraph 4
(2) There is geometrical isomerism VBT and CFT play very important role in determining the
(3) Both (a) and (b) geometryofcomplexcompound/ionandelectronicdistributionof
d-orbitals of central metal atom/ion in presence of given ligands
(4) None of these
respectively. A very important property of complex compound/
[Link]°fferentligands,thenhowmanygeometric
ion is to display isomerism.
isomers will be found for square planar [Pt PQRS]2+?
11. Which of the ligand can show geometrical as well as optical
(I) 1 (2)2
isomerism in square planar homoleptic complex?
(3) 3 (4) 4
7.108 Inorganic chemistry

third row transition elements and for more highly charged species.

•2,.I;Hi All the complexes having 4d8 and 5d8 configurations are mostly
squareplanarincludingthosewithweakfieldligandssuchashalide
ions. Square planar complexes can show geometrical isomerism
but they do not show optical isomerism due to the presence of
plane of symmetry.
18. Which of the following molecule has synergic bonding?
•3,MeF::= (4,EN:i (1) [Fe(W-C5H5)2] (2) [Rhc1 (Pph3)3]3+
(3) [Fe(Phen)3]3+
(4) All are having synergic bonding
12. Which of the following complex compound(s) is/are inner
19. Among the [Link], which has a square planar
orbital complex as well as low spin complex ion(s)?
geometry?
(1) INi(CN)6]4- (2) [Ag(S203)2]3-
( 1 ) [REcl(CO)(Pph3)2] (2) K3 [Cu(CN)4]
(3) [CuQVH3)4]2+ (4) [IrF6]3- (3) INi(CO)4] (4) K2[Zn(CN)4]
13. Which of the following compound(s) shows at least two 20. Which of the following complex is low spin?
types of structural isomerism,
(1) All are low spin complexes
( 1 ) Na[Fe(CN)2(H20)4] (2) [CO(SCN)(H20)5]C12 (2) INi(CO)4]
(3) [pdcloro2)ovH3)4]so4 (4) [crovH3)6] [coovo2)6] (3, ,Pto{H3,4]2+
14. In which of the following complex transition of electron (4) INiqu3)6]2+
occurs from one shell to other shell of central metal.
Paragraph 7
(1) [Co(H20)6]2+ (2) INi(CN)6]4- If in the mixed carbonyl, the other ligand is also 7t acceptor,
(3) [RhovH3)6]2+ (4) [Fe(H20)5NO]2+ it would compete with the ligand CO for gaining the metal
d„[Link],
15. Which of following hydrated complex ion has high intensity
thelesserwillbethestretchingvibrationfrequencyforCcObond.
colour in aqueous solution.
If pp3 is better 7t-acceptor than CO, then answer the following.
(1) [CO(H20)6]2+ (2) [Mn(H20)6]3+
21. Select the correct order ofMl bond order in the following
(3) [Mn(H20)6]2+ (4) INi(H20)6]2+
molecule and ions:
Paragraph 5 I. INi(CO)4] II. [CO(CO)4]©
Valence bond theory describes the bonding in complexes in terms Ill. [Fe(CO)4]2-
of coordinateueovalent bonds resulting from overlap filled ligand
(I)1>11>111 (2)I-11-Ill
orbitals with vacant metal hybrid orbitals. This theory explains
(3)11>111>1 (4)1<11<111
magnetic behaviour and geometrical shape of coordination
22. Select the correct order of stretching vibration frequency
compounds. Magnetic moment of a complex, compound can be
C-O bond in following molecules:
determined experimentally and theoretically by using spin only
I. INi(CO)4] II. INi(PF3)(CO)3]
formula.
Magnetic moment J;{==ZJ BM (where # = No. unpaired (1)1>11 (2)1<11

electrons). (3) I = 11 (4) cannot be predicted

16. The value of spin only magnetic moment for octahedral 23. Select the correct order ofcco bond length in the following
complex of the following configuration is 2.84 BM. The molecules:
correct statement is I. [MO(CO)3 (PF3)3] II. [MO(CO)3 (PC13)3]

(1) cr (in weak field ligand) Ill. [Mo (CO)3 (P(Me)3)3]

(2) d2 (in weak field and in strong field ligand) (1) I > 11 > Ill (2) Ill > I > 11
(3) d3 (in weak field and in strong field ligand) (3) 11 > Ill > I (4) I < 11 < Ill
(4) c/5 (in strong field ligand) Paragraph 8
17. Ni2+ cation combines with a uninegative monodentate ligand
Most of the metal carbonyls obey inert gas rule which states that
X© to form a paramagnetic complex INic14]2-. The number
the compounds in which the central metal atom appears to have
attained the configuration of a noble gas either by the sharing or
of unpaired electron(s) in central metal cation and geometry
by the transfe.r of electrons tend to be more stable.
of this complex respectively are
(1) One, tetrahedral . (2) Two, tetrahedral 24. Which of the following has lowest CcO bond order?
(3) One, square planar (4) Two, square planar (1) [Mn(CO)6]® (2) [Co(CO)4]°

Paragraph 6 (3) [Fe(CO)4]2- (4) INi(CO)4]

Square planar complexes are formed by d8 ions with strong field 25. Select the correct order of CcO bond length of the
ligands. The crystal field splitting Ao is larger for the second and following:
 Coordination compounds 7.109

I. [M(CO)3(PF3)] 11. [M(CO)3(PC13)] Ill. [M(CO)3(PMe3)] 35. Which of the following has lowest C-O bond length?

(1) 1<11=111 (2) 1>11>111 (1) [Fe(CO)4]2- (2) [Co(CO)4]®

(3) I-11-Ill (4) I-11>111 (3) INi(CO)4] (4) [Mn(CO)6]®

Paragraph 12
26. Which of the following has highest C-O bond length?
Coordinationcompoundplaysmanyimportantrolesinanimalsand
(1) [Mn(CO)6]® (2) [Co(CO)4]®
plants. They are essential in the storage and transport of oxygen, as
(3) [Fe(CO)4]2- (4) INi(CO)4] electronstransferagents,ascatalysts,[Link]
Paragraph 9 range of application in daily life takes place through formation
In the manufacture of iron, a gas (A) is formed in the zone of of complexes. Photographic fixing, qualitative and quantitative
combustion of the blast furnace. The gas (A) reacted with coke in analysis, purification of water, metallurgical extraction are some
the zone of fusion to form another gas (8). X moles of (B) reacts specific worth mentioning.
with iron at 200°C and 100 atm pressure to form a compound (C).
36. The complex [Fe(H20)5NO]2+ is formed in the brown ring
27. The d orbital(s) involved in the formation of the complex
(C) will be: :eds:efo:on::::eosuswshoe,:t;%:s:iyNPor;g:::I:::£3;:::::i:::;
(1) dz2 (2) dry and cJx2_y2
cone. H2S04. Select correct statement about this complex:

(3) dx2_y2 and dz2 (4) dx2_y2 (1) Colour change is due to charge transfer
(2) It has iron in +1 oxidation state and nitrosyl as NO©
28. The magnetic moment and effective atomic number of the
C, respectively, are (3) It has magnetic moment of 3.87 BM confirming three
unpaired electrons in Fe
(1) 4.93 and 36 (2) 0 and 34
(4) All the above are correct statements
(3) 0 and 36 (4) None
37. Extraction ofAg from sulphide ore and removal of uureacted
Paragraph 10
silver from photographic plate involve complexes:
The 7[ acceptor ligands are those which possess vacant 7t-orbitals
in addition to the lone pairs of electrons.
i;i:A:{%2N°)32}83£-n£:obt:th
29. Which of the following complex ion has lowest Ml bond
length?
{i}:A:{%2No,32}a],3[A[8A2#g3',22]]:-
(1) [V(CO)6]© (2) [Mn(CO)6]® 38. Lead poisoning in the body can be removed by
(3) Ni(CO)4 (4) Fe(CO)5
( 1) EDTA in the form of calcium dthydrogen salt
30. Which of the following complex ion has the highest CcO (2) Cis-platin (3) Zeisse's salt
bond length?
(4) DMG
(l) [V(CO)6]° (2)Ni(CO)4 39.S:;+gaansd;nc€]2+E°ctifreedpur:C.]#£;a;eet:rs,;:::i;:t[Link]S€:n2€
(3) Fe(CO)5 (4) [Mn(CO)6]©
31. Which of the following complex/ion has lowest C-O bond is prevented by
order? (1)Adding excess of K4[Fe(CN)6] when Cd2+ is only
(1) [V(CO)6]° (2)Ni(CO)4 precipitated
(3) Fe(CO)5 (4) [Mn(CO)6]© (2)Adding excess of KCN when Cu2+ forms stable
32. Which of the following complex/ion has lowest Ml bond
order? :8:(P¢ix)4[]g_u(CN)4]3-andcd2+fomsunstablecomp|ex

(2)Ni(CO)4
(3)£::iLen8d¥f¥oseswnhoetnf::+c:°m¥Lse£°mplex[Cu(CNS)4]2-
( 1) [v(co)6]©
(3) Fe(CO)5 (4)[Mn(CO)6]©
(4) All of the above
Paragraph 11
40. Arrange the following in order of decreasing number of
The 7T acid ligands donate their lone pairs to the metal to form a unpaired electrons:
normal a bond with the latter in addition to it, the vacant orbitals
I. [Fe(H20)6]2+ 11. [Fe(CN)6]3-
accept electrons from the filled metal orbitals to form a type of
Ill. [Fe(CN)6]4- IV.[Fe(H20)6]3+
7t-bond which suppliments the a bond.
(1) IV,I,11,Ill (2)I,11,Ill, IV
33. Which of the following has lowest Ml bond length?
(3) Ill, 11, I, IV (4) 11, Ill, I, IV
Paragraph 13
{; } F:{::}:: 2- {:} :Eon((cCo°))46]]o®
Complex compound with empirical formula Co5NH2.N02.Br2
34. Which of the following has lowest Ml bond order?
exist in two isomers A (red) and 8 (yellow) I mole of each A and
( 1 ) [Fe(CO)4]2- (2) [Co(CO)4]© 8 gives 2 moles of AgBr when treated with excess of AgN03.
(3) INi(CO)4] (4) [Mn(CO)6]®
[Link] Inorganic chemistry

41. A and 8 both can show. 4. Match the column.

( 1 ) Ionisation isomerism (2) Linkage isomerism igJ(:3j?-('JV.:- ex

crdrfum*' rapii ?ifeTas

`'; A 7g,

(3) Geometrical isomerism (4) Both (1) and (2)

a. Two unpaired electron P. INi(en,3]2+
42. Correct statement for A & 8 is:
b. No unpaired electron q. vF6]J-
(1) i3oth A and 8 contain ONO© as ligand
(2) A contains N02° while 8 contains ONO© as ligand. C, Optical isomerism r, INic12{SCN)4]4-
(3) A contains ON0° while 8 contains N02° as ligand. d. Inner orbital complex S. [Fe(cN)6r
(4) Both A and 8 contains N02° as ligands.
5. Match the column.
43. Correct statement forA & 8 is:
( 1 ) A and 8 both are paramagnetic i
colxpin`:.I `:` - :,¥`t*hafromtri

(2) A and 8 both are diamagnetic a. [Cr(H20)5Br]2+ P. Paramagnetic

(3) A is paramagnetic while 8 is diamagnetic b. [Cu(en)C14]Z- q. Shows geometrical
(4) A is diamagnetic while 8 is paramagnetic isomerism
C, [pt(Ox,2]2- r, Shows optical isomerism
d. [Fe(OH)4]° S. Do not follow BAN rule
t. Complexhavingsymmetrical
This section contains questions each with two colulnns I and 11.
_ bidentate ligand
Match the items given in column I with those in column 11.
1.
6. Match the column.

+ Colu
S,

g nunth¢r or unpajnd+
a.
[Ptc13(C2H4)]© P. Follow BAN ae
/+++ ^ eec r® I , y,```\s/rrsy

b. [co(cO)4]© q. Compl\ex involved in a. FTe(NH3)6]2+ P. 0

synergic bonding b. 5
[Mno4]© q.
C.
[v(cO,6]© r, Complex having highest C, [MnorH3)6]2+ r. I
bond length of Co ligand
S. 4
d. [Fe(cN)5c(cO)r3 S, Complex having lowest
7. Math the column.
bond length of co ligand. -
2. Match the complexes (in column I) with the type of ?Si

isomerism (in column 11).

11 + eren, lu-+g

a, K4INi(CN)4] and P. Number ofunpaired

a. [cravH3)4cl2] P. Optical INi(en)3]S203 . electrons
b. cis[Cr(en)2C12] q. Ionisation b. K4INiF6] and q. Magnetic b ehaviour
C, r. Coordination K,INiF`]
[Cr(en)2Or02)C1] SCN
C. K4[C00V02)6] and r, Hybridisation
d. [croun3)6] [cO(cN)6] S, Geometrical
[Fe(H20)6]C13
S, Geometry
•cp][Link],:I, , `` €olHmmll r
8. Match the complex (in column I) with the geometry
a. [Cr¢-C6H6)OJO)3] P. Coordination number
of ce^ntral metal is six. (in colurm 11).
.\ ^:- 2l-+(a

b. Bond order of all calunri'`F ` r,`:y cohimti^H

[Cr(C2H4)(CO)5] q. `acO rm-
tigand decreases (C¢mplex iSn) •r is*:
ue¢ kangertylexEon}
rz?t

C. [ptoro2)2(e%)2]2+ r. Stable according to

BAN rule a, INi(ding)2] P. Tetrahedral
d. Ir(SCN)(S04)quH3)4 S. Bond order of all b. [zncl4]2- q. Trigonal bipyramidal
M - L bond > I.0 C, r, Square planar
[C0qu02)6]4-
t. Ligands acts as
d. [Fe(CO)5] S, ' Square pyramidal
ambidentate
t. Octahedral
 Coordination compounds 7.111

9. Match the colulnn C. [Ma2bcde] r. Octahedral complex

VC¢rfuhiatV|,tt\;£`^€^Z;rz
compound
d. [Ma2b2Cd] S, Four geometrical isomers
a. Broun ring complex P. Octahedral
t. Only two geometrical
b. Calcium nitroprusside q. I,MM - OBM
isomer
C. Ca2[Fe(CN)6] r. UMM = Ji? BM 14. Match the column.
d. Complex ofAg formed S. No© ligand _ Ljf;

n\rl *,a
ex

during its extraction

a, [M(AB)3] P. Zero pair of enantiomers
10. Match the column.
` toyber£lthewithx) b. [M(AB)(CD)ef] q. Ten pair ofenantiomers `
Column I a olumn I, +
C, r, Four number of
[Ma4bc]
(Typ e of complex} (T hd€hftifefeufronri steredisomers
a f stereo isomer b
d. [Ma3b2C] S, Four geometrical isomers
as Socla q, prpcap+on\+tryml`
•:,|;-:I;A:,?`,(,r ,
(•yi;i:J:I : r, ,,-I: ;,\¥j , |' `J -`: ; :: i. : ; ;i;J`j`!.;|:,J-, * -- |

15. Match the column.

a, P. 6
[Ma2b2C2]"±#
5f3

SI:JJinn`m\`` J^ `,i:Sj`
. ap` . |` ,\ ,.:|(,?*#-£r€%

b. q. 2 a, [Ma3bcd] P. The number of

[M(AB)2ab]"±J# stereoisomers is two
C. r, 5
b. The number of pair of
[M(AA)2a2]"±L4 [Ma3b3] q.
enantiomer is zero
d. S. 3 r, The number of
[M(AB)a3br# C, [Mabedef]
t. 0 stereoisomers is five
d. [Mq2b2C2] S, The pair of enantiomer is
11. Match the column. One
Column| .;¥¥c t. The pair of enantiomer is
a, [Ma3bcdr Four optically active isomer fifteen
P.
16. Match the column.
b. [M(AA)b2Cd]"± q. Four geometrical isomer
5;|S7` v 1.

t : Crifrommr I ::\ i ^i;;.`iT

C. [M(AB)3r r. All geometrical isomers are
a. HexaGhloridop~ P. Monodentate ligand is pre-
optically active
latinate(2-) sent in complex/ion
d. [M(AB)b2C2]"± S. Two pair of enantiomer
b. Sodium diarmi q. Negative ligand is present
t. Two .optically inactive
netetrabromidocobaltate(Ill) in complex ion or molecule
isomer

Note: AA, BBS a, b, c, d are not having chiral centre. C, Tris (ethylenedi- r. Neutral 1igand is present
amine)copper(II) in complex ion/molecule
12. Match the column.
sulphate
• €®minri lI ,`(,: jr.2(
Column I d. Hexacarbonyl- S, Central atom of complex or
manganese ion is a member of
a. [M(AA)b2Cd] P. Complex molecule which
hypobromate 3d transition series.
shows optical isomerism
b. Only one cis and one trams t. Octahedral structure of
[M(ARA)b2C2] q.
isomer complex ion/molecule
C. [M(AA)2b2] r, Only one Gis and two trams 17. Match the column.
isomers : coininh I ; -J, se
J^`` )\`¥

d. [M(AA)3] S, Four geometrical isomers

a. [Fe(CN)6]3~ P. Optical isomerism
t. Complex in which any cis
isomer is optical active b. [Cr(en)2C12]® q. c72Sp3_hybridisation

13. Match the column. C, INion3)6]2+ r. cf2sp3 hybridisation

i ,``, *I
a..u

Coinmn 1]
$2*xfse;jygx,fsseisjjss;isjjsr,€3f;'.
a. [coF6]3- S. sp3c{[Link]
ffi *Q # -(-z

a, [Ma4bc] P. Six Gis isomers

b. [Ma2b2C2] q. Four trams isomers

7.112 Inorganic chemistry

18. Match the column. C, K3Fe(CN)6] r. Blue colour due to charge

;,, €®lumn 11 ^ ^s;J
an
transfer
a. Square planarcomplex d. K4[Fe(CN)6] S. Six electrons are present in
[Ptl2(en)] P.
t2g Orbitals
b. [PtovH3)212] q. central atom isamemberof3dtransitionseries t. BAN is 36
21. Match the column.

C, [Ptou3 )IN02)toy) NH20H] r. Complex whichshowsgeometri-calisomerism coluinm I " |;;-;;;-:;;:i

RE

a, [cr(cN)3oro2)3]4- P. [Link] orbital complex

d. b. [CO(C204)3]3~ q. Iamer orbhal complex

[Zn(gly)2] S, Non-planarcomplex
C, [Fe(EDTA)]® r,
t. Both neutral aswellasnega-tiveligandarepresentincom-plex
u--Ji8FIM
d. INi(en,3]2+ S, Shows optical activity

22. Match the column.

^* I, I
+8i

colrimn I JJ
J`Y;|: :'-:;;i +r ^--J ,€S,rij*I
J:`'i`,i,3y,-^

a, Mn040 P. [Link]
19. Match the column.

colunm^,I vtL ., •J;P`+,jtl., ,u ,-

b. cr042- q. Tetrahedral structure
a. [Cr(en)212]® P. Complex molecule/ion in C. Cr2072- r. Diamagnetic but colourful
which neutral ligand is species
presefit d. Cr02C12 S, +6 oxidation state on central
b. [PtoJH3)214] q. Complex which shows atom
geometrical isomeri sin t. all X-O bonds are identical
a, [Cr(en)3]3+ r, [Link] is present (where X is central atom)
in central atom of complex 23. Match the column.
molecule/ion
column|`£:`|^`tL^`3xp %z^

d. [Cr(Sly)3] S. Two geometrical isomers

a. [Fe(CO)4]2- P. Complex having lowest
bond length of CO ligand
t. Complex in which only
b. [v(cO,6]O q. Follow Sidgwick's rule
nitrogen atom acts as donor
atom ofEAN
C. K[Ptc13(C2H4)] r, Synergic bonding is
20. Match the column.
I ;jfv.~ ^ :`rz:€±Z:1:;fss;:±;S5;3±Sf<::AtaqigrmirlF?j^i`':;>:;^gp{`,89£9ee`",, €y^^
involved in complex/ion
•J€:,I,`` (1` gr
• 0 umm
d. preor2o)5No]so4 S, Complex having highest
a, [coqu,6,3+ P. [Link] bond length of CO ligand
t. Organoinetallic
b. Fe4[Fe(CN)6]3 q. Octahedral geometry
compound

24. Match the items given in column I with those in Column 11 and Ill.
ae
§88SsegJ,
C&homfl I a , Cutumn ll ,;),, +-18RE3,f?? C®lumn IH - /,rTr,:;,,€Z<,

grxp: +
8 z` ` f3/; R``\ ; 3
riff (; [Link]`pair€dEts`,¥jo} * q'`sh#pe & charac€d
a. [Feoro) (H,a){]2+ i. Zero P. sp3#, octahedral
b. [cOF6]3- ii. 3 q. dsp2, square planar
C. [CuOVH3)4]2- iii. 4 r. sp3, tetrahedral
d. INi(CO)4] iv. 1 S. Complex ion is formed in the brown ring test for
NO{e ion
 Coordination compounds 7.113

25. Match the items given in column I with those in Column 11 and Ill.

*$8ee v
Cofurmri` • €rimm`ri"Ierg+!#F\`J;,J-

i &g^v_Str)_6£'3::+?=^`^`\:`'``vr`\```t

a, [ptou3) qu2oH) oro2) toy)]® i. I P. Optical

b. [COC12qu3)4]® + ale•J ii. 3 q. Trams

[COC13 Ou3)3] + NHS

(Number of isomers obtained for the complex product)
C. [Cr(edta)]e iii. Zero r. Geometrical
d. iv. 2 S, None

[=)p<=]
e. H2N.
-,

[pt(giy)2] wheregly=glyc]nato ` e

:0: \o

26. Match the items given in column I with those in Column 11 and Ill.

3S#t, ~,"#E€y HS',I A,;+asc ` „ C0lumnl I

Column 11 ol uin`tlEEJ,
EN

-,`.;r*i¥*`%j\;; , : - yp ( 'c<gQ

:: ¥kysfal fiSid theory :`-)#Si

a, Fe+2 (In weak octahedral field ligand) i. t42g'egl P. 4

b. Fe+2 (In strong octahedral field ligand) ii. t42g,eg2 q. 3

C. Mn3+ (In weak octahedral field ligand) iii. t62g*ego I. Zero

d. Mn3+ (In strong octahedral field ligand) iv, t32g,egl S, 2
e. Cr3+ (In weak and strong octahedral field ligand) V. f2g , ego
27. Match the items given in column I with those in Column 11 .and Ill.
[ column I a( ':;<`J,()9`; ),:`h

colurm A H alumn\
€,
Compound nic configrfieldthe mg

!a.
[Cr(H20)6]2+(whenA<p) i. (e2, t23) P. ro.6 Ao
b. [Fec14]e (When A < p) ii. (e2,tio) -1.6 Ao+P
q.
C. [Fequ2-(WhenA<p) iii. (t42g,ego, I, 7jrff!fJ

d. [Crou3)6]2+(WhenA>p) iv, (t32g,eg', S, -I .2 At

4. Give the number of ligands which are monodentate as well

as anbidentate.
Naming and Terminology 8N,C2042-,S22-,N02®,8CN,SCN®
1. Give the number ofligand(s) in which donor atom is onlyN. 5. Give the number of strong field ligand(s) from the following:
NH2CH2COO©, en, dien, Py, EDTA, ph NH3,en,C1°,CH3C00°,8N,CO,N02©
2. Give number of nor-classical ligand which are negative 6. Give the number of weak field ligand(s) from the following:
li8ands.
© s2-,8H,C1°,H20,Py,N02°,N03®
CN, S2032~, C3H5°, C5H5©. 7. The sum of primary and secondary valencies of chromium
3. Give the number of ligands which are negative as well as in the complex CrBr3.6NH3 is
flexidentate. 8. Find the number of ligand(s) which is/are chelating.
C032-, CH3COO©, X°, H°, S042- en, C2042-, acac, DMG, gly, ph
7.114 Inorganic chemistry

9. Find the number of ligand(s) which is/are polydentate ligand. 26. Give the ratio of geometrical isomers in [M(AA)2b2] and
en, ding, dien, EDTA optical isomers of [M(AA)3].

10. How many coordinated water molecule(s) is/are present in 27. Give the number of geometrical isomer in [Pt(gly)2].
brown ring complex? 28. Give the total number of possible isomers of
11. Sodium nitroprusside is used to test S2- ion. How many
[Col2(CN)Oun3)en].
CN© ion acts as ligand in the compound?
29. Give the total number of possible isomers (c!.s-/r¢#s and
12. Give the number of ligand(s) which is/are ambidentate and optical) of [Crc12 en2]©.
bidentate.
30. Give the total number of possible structural isomers of the
S©CN,8CN,S2032-,C2042-,S2~ 1111
compound [Cu(NH3)4] [Pt 14] .
13. Give the number of ligand(s) which is/are non-classical
31. Give the number of total possible coordination isomers in
ligand.
[ptoun3)4] [cu(Br)4].
Co, No, C2H4, C3H5e, H©
32. Give the number of total possible ionisation isomers in
14. Give the number of ligand(s) which are monodentate, neutral
as well as non-classical ligand. [PtovH3)4C12]Br2.
0 33. Give the ratio of trams-isomers in [M(AA)b2C2] (A) and
CO, CN, S2032-, PF3
[Ma4b2] (a), respectively.
15. Give the number of ligands which are non-classical ligand
and 7t donor as well as 7t acceptor ligand. Hybridisation, VBT, CFT and Applications
CO, PH3, PF3> C3H5©. C5H5© 34. In hexacyanidomanganate(II) ion the Mn atom assumes
16. What are the values of " and # in the anionic species d2sp3-hybrid states. Then the number of unpaired electrons
[V(CO)m]"-,ifitisfollowingSidwickEANruleandhaving in the complex is:
octahedral shape? 35. Give the number of unpaired electron(s) in the complex ion
17. Consider the following carbonyl complex compounds [coc,6,3-.
(I)Hxcr(CO)5 (II) C02(CO)y (Ill)MO(CO)z 36. Predict the number of unpaired electrons in a tetrahedral cf
ion and in a square planar c77 ion.
then calculate the value of
(¥) is: 37. Give the number of unpaired electron presen.t in the
18. If I is total number of 7r bonds in ph (I,10-N, N- d-orbitals (whose lobes are present along the axis) for the
phenanthroline) and )/ is total number of lone pair e-'s in complex [Co(SCN)4]2~.

ph and cr-nitroso-A-naphthol. Then calculate the value of 38. Give the number of 3d electrons occupied in f2g orbitals of
hydrated Cr3+ ion (octahedral).
(=). 39.#4%ryunpairedelectronsarepresentinegorbita|of
Isomerism
19. Give the total number of possible isomers of [ZnBr2F2]2-. 40. How many electrons are present in c7z2 orbital of INi(gly)2]?
20. Give the number of pair of enantiomer of [Ma2b2cd]. 41. Give the total number of /2g and eg electrons in [NiF6]2-.
21. Give the total number of isomer of [Be(gly)2].
42. How many electrons are present in d-orbitals which are
22. How many pairs of enantiomers are possible for
present along the axis in [Ti(H20)6]3+?
[M(AA) (BC)de]? 43. If Hund's rule is violated, then how many unpaired electrons
23. Find the number of geometrical isomers in are present in [Cr(N113)6]3+ complex ion?
[Co(en)(Pn) oVo2)2]. 44.Givethenumberofunpairedelectronsinf2gsetofd-orbitalsin
*
[CO(H20)3F3] Complex.
en = H2£H2-i:: pn = NH2+H2|=TNH2 45. How many maximum atom(s) is/are present in same plane
ofcr(CO)6?
24. Write the sum of geometrical isomers in
© 46. Find out the number of hydrogen bonds present in the
structure of the nickel dimethylglyoxime complex.
;Et{Ft{g]#g::=;,]=oo,2]Comp]exandstereo£Somers
47. How many e-'s are present in /2g set of d-orbitals of central
25. Write the sum of geometrical isomer in [Ma2b2c2] complex
and stereoisomers in [M(AB)3] complex. metal cation in [Fe(H20)5NO]S04 brown ring complex.
 Coordination compounds 7.115

JEE ADVANCED 6. As per IUPAC nomenclature, the name of the complex

[CO(H20)40VH3)2]C13 is
Single Correct Answer Type • ( I ) Tetraaquadiaminecobalt(III) chloride

. 1. The correct structure of ethylenediamineteraacetic acid (2) Tetraaquadiamminecobalt(Ill) chloride

(EDTA) is (3) Diaminetetraaquacobalt(Ill) chloride
(4) Diamminetetraaquacobalt(Ill) chloride
•1,::::=::>-H-CH-N(::::::: (IIT-JEE 2012)
7. The colour of light absorbed by an aqueous solution of
CuS04 is
(2)::::>CH2CH2N<::: ( 1 ) orange-red (2)blue-green
(3) yellow (4)violet
(IIT-JEE 2012)
8. [Nic12{P(C2H5)2 (C6H5)}2] exhibits temperature dependent
(3)::::=::>CH2CH2N<::I::::
:oao¥d::£actfonbegheaovi°ei:estoo¥aNT2a+i:t]fa/:£=ra£:£C:;,c`:i:
COOH diamagnetic states are respectively
/
( 1 ) Tetrahedral and tetrahedral
(4)HooC-H2C\f:+H-N<:H2_COOH
(2) Square planar and square planar
H/Hooc/CH2 (3) Tetrahedral and square planar
(4) Square planar and tetrahedral
(IIT-JEE 2012)
(IIT-JEE 2010) 9. Which of the following complexes is not expected to exhibit
2. The ionisation isomer of [Cr(H20)4C10ro2)]Cl is optical isomerism?
( I ) [Cr(H20)4(02N)]C12 (1) [Co(en)2C12]® (2) [CO0VH3)3C13]
(2) [Cr(H2o)4C12]oro2) (3) [CO(en) OVH3)2C12]® (4) [Co(en)3]3+
(3) [Cr(H20)4Cl(ONO)]Cl (JHE Advanced 2013)
(4) [Cr(H20)4C12(N02)]H20 10. Consider the following complexes ions, P, Q and R
[Link] 2Oio] P = [FeF6]3-, Q = [V(H20)6]2+ and R = [Fe(H20)6]2+
3. The complex showing a spin-magnetic moment of 2.82 BM The correct order of the complex ions, according to their
is
spin ohly magnetic moment values (in BM) is
(l)Ni(CO)4 (2)INic14]2-
(1)R<Q<P (2)Q<R<P
(3) NiQ'Ph3)4 (4)INi(CN)4]2-
(3)R<P<Q (4)Q<P<R
(IIT-JEE 2010)
(JHE Advanced 2013)
4. Geometrical shapes of the complexes formed by the reaction 11. An excess ofAgN03 is added to loo mL ofa 0.01 M solution
of Ni2+ with C1°, CN° and H20, respectively, are of dichlorotetraaquachromium(Ill) chloride. The number of
( I ) Octahedral, tetrahedral and square planar moles of Agcl precipitated would be
(2) Tetrahedral, square planar and octahedral (1) 0.003 (2) 0.01
(3) Square planar, tetrahedral and octahedral (3) 0.001 (4) 0.002
(4) Octahedral, square planar and octahedral (JEE Advanced 2013)
(IIT-JEE 2011) 12. The equation which is balanced and represents the correct
5. Among the following complexes (K-P) product(s) is
Excess NaoH
K3[Fe(cN)6] (K), [cOovH3)6]cl3 aj), (1) [Mg(H20)6]2+ + (EDTA)4-
Na3 [Co(oxalate)3] (M), INi(H20)6]C12qu), [Mg(EDTA)]2+ + 6H20

[pt(cN)4] (o) and [zn(H2o)6] oro3)2a]) (2) CuS04 + 4 KCN -K2[Cu(CN)4] + K2S04
The diamagnetic complexes are (3) Li20 + 2 Kcl -2Licl + K20
(1)K,L,M,N (2)K,M,O,P (4) [CoC10JH3)5]® + 5H® + Co2+ + 5NH4® + Cl©
(3)L,M,O,P (4)L,M,N,O (JHE Advanced 2014)
(IIT-JEE 2011)
7.116 Inorganic chemistry

13. The number of geometric isomers that can exist for square 3. The correct option(s) regarding the complex [Co (en) (NH3)3
planar [Pt(Cl)®y)OJH3)OJH20H)]® is toy = pyridine) : (H20)]3+ (en = H2NCH2CH2NH2) is (are)
(1)2 (2)3 (I) It has two geometrical isomers
(3) 4 (4) 6 (2) It will have three geometrical isomers if bidentate `en' is
(JEE Advanced 2015) replaced by two cyanide ligands
14. Among INi(CO)4], INic14]2-, [Co0VH3)4C12]Cl, Na3[COF6], (3) It is paramagnetic
Na202 and CS02, the total number of paramagnetic
(4) It absorbs light at longer wavelength as compared to.
compounds is
[Co (en) OVH3)4]3+ (JEE Advanced 2018)
(1) 2 (2)3`
4. Choose the correct statement(s) among the following:
(3) 4 (4)5 (JEE Advanced 2016)
( 1) [Fec14]-has tetrahedral geometry.
[Link]+:::s::tcrt£]evse:y:Treeamm°n]acomplexesofNi2+,pt2+and
(2) [Co(c#)(NH3)2C12]+ has 2 geometrical isomers.

(1) octahedral, square planar and tetrahedral (3) [Fec14]- has higher spin-only magnetic moment than
[Co(e%)OVH3)2C12]+.
(2) square planar, octahedral and tetrahedral
(3) tetrahedral, square planar and octahedral (4) The cobalt ion in [Co(e„)(NH3)2C12]+ has sp3c72
hybridization. (JEE Advanced 2020)
(4) octahedral, tetrahedral and square planar
(JEE Advanced 2016) 5. The pair(s) of complexes wherein both exhibit tetrahedral
16. The calculated spin only magnetic moments of [Cr(NH3)6]3+ geometry is(are)
and [CuF6]3-in BM, respectively, are (Atomic numbers of (Note: py = pyridine Given: Atomic numbers of Fe, Co, Ni
Cr and Cu are 24 and 29, respectively) and Cu are 26, 27, 28 and 29, respectively)

(1) 3.87and2.84 (2) 4.90 and 1.73 (1) [Fec14]~ and [Fe(CO)4]2-

(3) 3.87 and 1.73 (4) 4.90 and2.84 (2) [cO(co)4r and [cocl4]2-
(JEE Advanced 2021) (3) INi(CO)4] and INi(CN)4]2-

Multiple Correct Answers Type (4) [Cutoy)4]+ and [Cu(CN)4]3-

I. The pair of coordination complexes/ions exhibiting the (JEE Advanced 2021)

same kind of isomerism is (are)
(1) [CrovH3)5Cl]C12 and [CrovH3)4C12]Cl
Linked Comprehension Type
(2) [CO(NI13)4C12] ® and [PtovH3)2(H20)Cl]®
Paragraph 1
(3) [CoBr2C12]2~ and [PtBr2C12]2- The coordination number of Ni2+ is 4.
(4) [PtovH3)30V03)]Cl and [PtovH3)3C1]Br Nic12 + KCN(excess) i A (cyano complex)
(JEE Advanced 2013)
Nic12 + conc. HC1 (excess) + 8 (Chloro complex)
2. Addition of excess aqueous ammonia to a pink coloured
aqueous solution of MC12.6H20(X) and NH4Cl gives an
1. The IUPAC name ofA and 8 are
octahedral complex Y in the presence of air. In aqueous ( I ) potassium tetracyanonickelate (11),
solution, complex Y behaves as 1 : 3 electrolyte. The reaction potassium tetrachloronickelate (11).
of X with excess Hcl at room temperature results in the (2) tetracyanopotassiumnickelate (11),
formation of a blue coloured complex Z. The calculated spin tetrrachloropotas siumnickelate (11).
only magnetic moment of x and Z is 3.87 B.M., whereas it (3) tetracyanonickel(II) tetrachloronickel(II)
is zero for complex Y. (4) potassium tetracyanonickel(II), tetracholoronickel (11).
Among the following options, which statement(s) is(are) 2. Predict the magnetic nature ofA and 8:
correct? ( 1 ) Both are diamagnetic.
(1)The hybridization of the central metal ion in Y is (2) A is diamagnetic and 8 is paramagnetic with one unpaired
d2JP3. electron.
(2) Z is a tetrahedral complex (3) A is diamagnetic and 8 is paramagnetic with two unpaired
(3) Addition of silver nitrate to Y gives only two equivalents electrons.
of silver chloride. (4) Both are paramagnetic.
(4) When X and Z are in equilibrium at 0°C, the colour of the 3. The hybridisation of A and 8 are
solution is pink (JEH Advanced 2017)
(I) dsp2 , sp3 (2.) sp3 , sp3
(5) dsp2 , dsp2 (4) sp3 d2 , d2sp3
(IIT-JEE 2006)
 Coordination compounds 7.117

Paragraph 2 2. Match each coordination compound in Column I with an

An aqueous solution of metal ion Ml reacts separately with appropriate pair of characteristics from Column 11 and select
reagents Q and R in excess to give tetrahedral and square planar the correct answer using the code given below the lists.
complexes, respectively. An aqueous solution of another metal
€®lrigiv,n I , , Cfllinrmm:H
ion M2 always foms tetrahedral complexes with these reagents.
Aqueous solution of M2 on reaction with reagent S gives white a' [CrQqH3)4C12]C1 P. Paramagnetic and
exhib its ionisation
precipitate which dissolves in excess of S. The rea'ctions are
summarised in the schem? given below: isomerism
I [Ti(H2o)5ci]oro3)2
b. q. Diamagnedc and
SCHEME:
exhibits cis-trams
Tetrahedral-Ml+Squareplanar
excess
isomerism
C, [pt(en) orH3)cl]No3 r. Paramagnetic`and
Tetrahedral<±M2L+Tetrahedral exhibits cis~trans
excess
isomerism
S stoichiomeinc ainount
d. [Coqu)4qu03)2]N03 S. Diamagnetic and
i S exhibits ionis ation
Whiteprecipitate=precipitatedissolves isomerism
4. M1, Q and R, respectively are

(1) Zn2+, KCN and HC1 (2) Ni2+, H`Cl and KCN
(3) Cd2+, KCN and-Hcl (4) Co2+, Hcl and KCN
5. Reagent S is
( I ) K4[Fe(CN)6] (2) Na2HP04
(3) K2Cr04 (4) KOH
(JEE Advanced 2014)
(JEE Advanced 2014)
3. Match the catalysts to the correct processes:
Paragraph 3
Ctltal+St
The reaction of K3[Fe(CN)6] with freshly prepared Fes04 a, Ticl? Wacker process
solution produces a dark blue precipitate called Tumbull's blue. b. Pdc1' ii. Ziegler-Natta polymerization
Reaction of K4[Fe(CN)6] with the Fes04 solution in complete
C, Cucl, iii. Contact process
absence of air produces a white precipitate X, which turns blue in
d. V205 iv` Deacon 's process
air. Mixing the Fes04 solution with NaN03, followed by a slow
addition of concentrated H2S04 through the side of the test tube (1) a. -iii., b. -ii., c. -iv., d. -i.
produces a brown ring. (JEE Advanced 202l) (2) a. -ii., b. -i., 6. -iv., d. -iii.
6. Precipitate X is (3) a. -ii., b. -iii., c. -iv., d. -i.
(I) Fe4[Fe(CN)6]3 (2) Fe[Fe(CN)6] (4) a. -iii., b. -i., c. -ii., d. ~ iv.

(3) K2Fe[Fe(CN)6] (4) KFe[Fe(CN)6] (JE;E Advanced 2015)

4. Match each set of hybrid orbitals from List-I with
7. Among the following, the brown ring is due to the formation
complex(es) given in List-II.
of
• \ *fis`t
( E i§tur
(1) [FeoJO)2(S04)2]2+ (2) [Feo¢O)2(H20)4]3+
p. dsp2 1. [FeF6]4~
(3) [Feovo)4(so4)2] (4) [Feavo)(H2o)5]2+
Q. sp3 2. [Ti(H20)3C13]
Matrix Match Type R. sp3d2 3. [crorH3)6]3+
I. Match the complexes in Column I with their properties s. d2sp3 4. [Fec14]2-
listed in Column 11.
^ £inHmn I 5. Ni(CO)4
€fl||u"flu'H^ i, ;1+v€£;`:`g 6. INi(CN)4]2-
a, [cOounq)4 (H,o),] cl, P. Geometrical isomers . The correct option is
b. [Pto¢113)2C12] q` Paramagnetic (1) P + 5; Q i 4, 6; R + 2, 3; S + I
€. [CO(H20)5Cl]Cl r, Diamagnetic (2) P i 5, 6; Q + 4; R i 3; S + I, 2
(3) P i 6; Q + 4, 5; R + I; S + 2, 3
a. INi(H20)6]C12 S, Metal ion with +2
(3) P + 4, 6; Q + 5, 6; R + 1, 2; S + 3
oxidation state
(JEE Advanced 2018)
alT-]EE 2007t
7.118 Inorganic chemistry

Numerical Value Type 6. For the octahedral complexes of Fe3+ in SCN°

(thiocyanato-S) and in CN° 1igand environments, the
1. The volume (in mL) of 0.1M AgN03 required for Complete
difference between the spin-only magnetic moments in
precipitationofc1®ionspresentin30mLof0.01Msolution Bohr magnetons (when approximated to the nearest integer)
of [Cr(H20)5C1]C12, as silver chloride is close to
is . [Atomic number ofFe = 26]
(IITjinll) (JEE Advanced 2015)
2. EDTA4- is ethylenediamine tetraacetate ion. The total 7. If the freezing point of a 0.01 molal aqueous solution of a
nunoer of N-Co-O bond angles in [Co(EDTA)]-I complex cobalt (Ill) chloride-ammonia complex (which behaves as a
ion is (JEE Advanced 2013) strong electrolyte) is -0.0558°C, the number of chloride(s)
3. In the complex acetylbromidodicarbonylbis in the coordination sphere of the complex is
(triethylphosphine) iron(II), the number of Fe{ bond(s) [K/ofwater=1.86Kkgmol~]]
is (JEE Advanced 2015) (JHE Advanced 2015)
4. Among the complex ions, [Co(NH2CH2CH2NH2)2C12]©>
8. The number of geometric isomers possible for the complex
[Crc12(C204)2]3-, [Fe(H20)4(OH)2]+, [FeovH3)2(CN)4]°,
[COL2C12]- (L = H2NCH2CH20-) is-
[COO{H2CH2CH2NH2)2(N113)C1]2+ and [CO0VH3)4(H20) (JHH Advanced 2016)
Cl]2+, the number of complex ion(s) that show(s) cis-trams
9. Total number of cis N-Mn-Cl bond angles (that is, Mn - N
isomerism is
and Mn - Cl bonds in cis position) present in a molecule of
(JEE Advanced 2015)
5. In dilute aqueous H2S04, the complex diaquodioxalatofer- Cis-[Mn(en)2C12] Complex is_
rate(II) is oxidized by Mn04°. For this reaction, the ratio of (en = NH2CH2CH2NH2) (JEH Advanced 2019)
the rate of change of [H©] to the rate of change of [Mn04°] 10. The total numbers of possible isomers for [PtQVH3)4C12]Br2
is is
(JEE Advanced 2015) (JEE Advanced 2021)

Answers Key
EXERCISES 101. (2) 102. (i) 103.(3) 104.(1) 105.(2)
106. (1) 107. (2) 108.(3) 109.(2) 110.(4)
Single Correct Answer Type
111. (4) 112. (2) 113.(3) 114.(2) 115.(4)
1. (2) 2. (4) 3. (1) 4. (4) 5. (3) 116. (2) 117. (1) 118.(3) 119.(1) 120.(1)
6. (2) 7. (1) 8. (4) 9. (1) 10. (2) 121. (1) 122. (1) 123.(3) 124.(2) 125.(1)
11. (2) 12. (1) 13. (3) 14. (3) 15. (4) 126. (3) 127. (2) 128.(1) 129.(4) 130.(2)
16. (1) 17. (2) 18. (1) 19. (3) 20. (1) 131. (1) 132. (1) 133.(3) 134.(1) 135.(1)
21. (1) 22. (2) 23. (1) 24. (3) 25. (2) 136. (4) 137. (3) 138.(1) 139.(3) 140.(1)
26. (3) 27. (2) 28. (i) 29. (3) 30. (3) 141. (4) 142. (3) 143.(3) 144.(1) 145.(2)
31. (3) 32. (3) 33. (4) 34. (3) 35. (4) 146. (2) 147. (3) 148.(1) 149.(4) 150.(2)
36. (2) 37. (1) 38. (1) 39. (I) 40. (4) 151. (2) 152. (1) 153.(2) 154.(3) 155.(3)
41. (2) 42. (2) 43. (4) 44. (2) 45. (4) 156. (2) 157. (2) 158.(2) 159.(3) 160.(1)
46. (2) 47. (2) 48. (3) 49. (1) 50. (3) 161. (1) 162. (4) 163.(1) 164.(1) 165.(4)
51. (1) 52. (2) 53. (3) 54. (3) 55. (3) 166. (2) 167. (1) 168.(2) 169.(1) 170.(3)
56. (3) 57. (3) 58. (2) 59. (1) 60. (2) 171. (1) 172. (3) 173.(1) 174.(4) 175.(1)
61. (3) 62. (2) 63. (1) 64. (2) 65. (3) 176. (1) 177. (2) 178.(3) 179.(1) 180.(1)
66. (2) 67. (2) 68. (2) 69. (2) 70. (i) 181. (3) 182. (3) 183. (1)
71. (3) 72. (3) 73. (3) 74. (2) 75. (4) ,
76. (2) 77. (2) 78. (2) 79. (3) 80. (3) Multiple Correct Answers Type
81. (4) 82. (4) 83. (4) 84. (4) 85. (1)
86. (1) 87. (2) 88. (4) 89. (1) 90. (4)
91. (3) 92. (2) 93. (2) 94. (2) 95. (3)
96. (4) 97. (3) 98. (4) 99. (2) 100. (4)
 Coordination compounds 7.119

13. (1, 2, 3) 14. (2, 3, 4) 15. (I,4)

19. P, q, r, S P, q, r' S p, r' t- q, r, S -
16. (2,3,4) 17. (2, 3, 4) 18. (1,2,3)
19. (1, 2, 3) 20. (2,3) 21. (2, 3) 20. p, q, s, tp, q, r, s, t P,q p, q, s' t - -
22. (I) 23. (2, 3) 24. (I, 2, 3, 4) 21. q,r q,S q,S P, r' S
- -
t q, r, Sp, q, r, s' t - -
25. (1, 4) 26. (1, 2, 4) 27. (1,2,3,4)
22. p, q, r' t p, q, r, s, P,
28. (2, 3, 4) 29. (1, 2, 4) 30. (2,4)
31. (2, 3, 4) 32. (2,3) 33. (1, 2, 4)
23. q, r' s' t p, q, r, t r't r - -
34. (3, 4) 35. (1, 2, 3) 36. (2, 3, 4) 24. ii-p, s iii-p iv-q i-r
37. (1, 3, 4) 38. (I,2) 39. (i,2) 25. ii-r i-q iv-p iii-s iv-r
40. (2, 3, 4) 41. (2,3) 42. (1, 2, 3, 4)
43. (1, 2, 3, 4) 44. (1,2,3) 45. (1,2,4)
26. ii-p iii-r iv-p i-s V-q
46. (1,2) 47. (1,2,3) 48. (1,2,4) 27. iv-p i-r ii-s iii-q
49. (1,2) 50. (I,2,3) 51. (2, 3, 4)
52.(2,3,4) 53. (I,2,3) Numerical Value Type
54. (1, 2)

1. (4) 2. (3) 3. (3) 4. (4) 5. (5)

Linked Comprehension Type
6. (5) 7. (9) 8. (6) 9. (2) 10. (5)
I.(1) 2.(2) 3. (2) 4. (3) S. (2)
11. (5) 12. (1) 14. (4) 14. (2) 15. (2)
6. (2) 7. (3) 8. (I) 9. (2) 10.(1)
16.(6,1) 17.(2.4) 18.(3.5) 19.(2) 20. (2)
11.(3) 12.(1,4) 13.(2,3,4)14.(3,4) 15.(2)
21. (2) 22. (5) 23. (5) 24. (8) 25. (9)
16. (2) 17. (2) 18. (4) 19. (1) 20. (3)
21. (4) 22. (2) 23. (4) 24. (3) 25. (1) 26. (1) 27. (2) 28. (8) 29. (3) 30. (4)
26. (3) 27. (1) 28. (3) 29. (1) 30.(I) 31. (4) 32. (3) 33. (2) 34.-(1) 35. (4)
31.(1) 32.(I) 33. (3) 34. (4) 35. (4) 36.(4,I) 37.(0) 38. (3) 39. (0) 40. (2)
36. (4) 37. (4) 38. (1) 39. (2) 40. (1)
41. (6) 42. (0) 43. (1) 44. (2) 45. (9)
41. (4) 42. (3) 43. (3)
46. (2) 47. (5)
Matrix Match Type
ARCHIVES

[Link]. a b C d e f JEE Advanced

1. q P, q, r q P, q, S
- - Single Correct Answer Type
2. S P q r - - 1. (3) 2. (2) 3. (4) 4. (2) 5. (3)
3.. q, r' S P, q, r' S P,r p, r, t - - 6. (4) 7. (I) 8. (3) 9. (2) 10. (2)
4. P, q, r S, P q,S
- - 11. (3) 12. (4) 13. (2) 14. (2) 15. (1)

5. P,S p, s, t s,t P,S

- - 16. (1)

6. S P q - - - Multiple Correct Answers Type

7. r'S P P - - - I. (2,4) 2. (1,2,4) 3.(1,2,3)
8. r P t q - - 4. (1,3) 5.(1,2,4)

9. P, r' S P, q, S P,q q - - Linked Comprehension Type

10. P r t P - - 1.(1) 2.(3) 3. (1) 4. (2) 5. (4)
11. q p, q, s' t P, r' S p, q, s, t - - 6. (3) 7. (4)
12. p, s, t p, r' t p, q, t P - - Matrix Match Type
13. r't q,r P, r, S q,r - - 1. (a i p, q, s; b i p, r, s; c i q, s; d i q, s)
14. r'S q S P - - 2. (2) 3. (2) 4. (3)
15. r'S P,q t S - - Numerical Value Type
16. p, q, t p, q, r' s' t r' s, t p, r' s, t - -
1. (6) 2. (8) 3. (3) 4. (6) 5. (8)
17. q,r P, q, r r,S r,S - - 6. (4) 7. (1) 8. (5) 9. (6) 10. (6)
18. p,t p, r' t p, r' t q,S
- -