Coordination Chemistr

d-b ase add uct s (examples) , dou ble sal ts

Syllabus: Coo rdin ate bon din g: Lewis aci

salt s, We rne r the ory of coo rdin ation com pou nds . Am bid ent ate and
and complex

che late com plexes. IUP AC nom enc latu re of coo rdi nat ion com pou nds
polydentate ligands ,

met al cen ters). Coo rdin atio n num ber s, con stit utio nal iso me rism .
(up to two
ahedral complexes.
Stereoisomerism in square planar and oct

the following aspects of th e

Objectives of this lecture is to cover
syllabus:

• Molecula5 com po un ds
+
Complex sal ts or
Do ubl e sal ts
Co ord ina tio n
com po un ds
I
. +
Perfect Imp erfe ct
complex complex

t and rel t · .
j
• Concept of ·stability con stan
· a mg 1t to the def init ion s of f
e fi t d
P r ec an imperfect complexes.
• Some basic definitions
(1) Ligand; (2) Coordination num ber
• Classification of lig and s
 11vu ~u :,::,1ttL h 1::, N U l Hl
NG

COOBDINATIONCIIElVIISTBY
M an y m et al sa lts in wh ic h
no rm al va le nc ie s of th e m
sa tis fie d m ay co m bi ne wi th et al at om s we re fu lly
ot he r m ol ec ul es an d is ca pa
ex ist en ce to fo rm m ol ec ul bl e of in de pe nd en t
ar co m po un ds . Two di sti
m ol ec ul ar co m po un ds we re nc t ty pe s of su ch
re co gn ize d - ( 1) Do ub le sa lts
co m po un ds or co m pl ex co ; (2) Co or di na tio n
m po un ds .

0 W ha t ar e do ub le sa lt s or la
tt ic e co m po un ds ?
Ans: A do ub le sa lt is
an ag gr eg at e of tw o si m pl e
sa lt s in a ce rt ai n pr op or ti in or ga ni c
on an d th e ag gr eg at e si m pl
sp li ts in to th e co n st it u en t y
io ns in so lu ti on . It in di ca te s th at
th e ag gr eg ate m ai nt ai ns th
e in di vi du ali ty of th e co ns
do ub le sa lt sh ow s its di st tit ue nt sa lts . Th us a
in ct en tit y in th e so lid cr
lo se s its id en tit y in so lu tio ys ta lli ne st at e bu t
n.

In th e so lu tio n, ex ist en ce of
th es e io ns ca n be pr ov ed ch em
ica lly
M oh r's Sa lt:

Ex am pl e of Do ub le sa lts an
d Co m pl ex sa lts
(a) Po ta sh alu m : K2S04. Ab (S0
4)3. 24 H2 0
(b) M oh r's sa lt: (NH4)2 S0 4. Fe
S0 4. 6H 20
(c) Ca rn ali te: KCl. MgCb. 6H
20 Do ub le Sa lts
(d) Ch ro m e alu m: K2S04. Cr2
(S04)3. 24 H20
 - - - - -- ---- -- .... - -----••- - • I

(0 Potassium ferrocyanide: [Link](CN)2 or K4[Fe(CN)6]

Complex
(g) Potassium ferricyanide: [Link](CN)3 or K3(Fe(CN)6]
salts
(h) Potassium chloroplatinate: 2KCl.PtC14 or K2fPtCl6]

( (i) Prussian blue: [Link](CN)[Link](CN)3 or KFe[Fe(CN)6]

8 What are complex salts or Coordination co pounds?

Ans: In a complex salt, the individual identities of the constituent salts are
generally lost. Thus a complex salt on being ionised cannot produce all the
constituent ions in solution. The behaviour of a complex salt is illustrated by
taking the e.g. of K4[Fe(CN)6]
Ionises Fe 2+
(water)

~ - 4K+ + [Fe (CN)5)4-

+
Free ion (+ve test) Tests Fe 2+ (X)
CN- (X}
[Fe (CN) 6)4-

Coordinate bond

The solution of K4[Fe(CN)6] fails to respond to the common chemical test for
2
CN- and _Fe + ions .. It gives the test for the complex ion [Fe (CN) 6J4- whose
property Is totally different from those of the constituent ions Fe2+ and CN-. In
fact, .the complex ion ferrocyanide is stable both in the solid and in the
solut10n phase. The complex ions capable of maI·nta, ·
[Link] · d ep en d en t
· In
th eir
 ~;::~::~~:. .i: ;~~~■-~j~;·
1
11

~olid and the solution phase are written within a [ ], for

e.g. [Fe(CN)6] 4 - .

-..f K4 [Fe (CN)6] 4 - [Fe (CN)6]4 -

\...__~ - - ~)
y
.
-----. Coord.1nation
Ionisation sphere sp h ere Coordination entity

C, What are coordination compounds?

Ans: A coordination compound is any compound that contains a
coordination entity. A coordination entity is an ion or neutral molecule
that is composed of a central atom (usually that of a metal) to which 1s
attached a surrounding array of other atoms or groups of atoms , each of
which is called a ligand. (IUPAC recommendations, 2005)

0 What are perfect and imperfect complexes?

Ans: Some complex ions like [Cd(CN)4]2- as in K2[Cd(CN)4] & [Ni(NH3)5)2 + as in

[Ni(NH3)5]Cb etc. respond to some of the chemical test for the metal ions &
involved ligands. Thus, K2(Cd(CN)4] ionizes sufficiently to allow the detection
of Cd2+ as CdS by passing H2S. CN- can also be chemically detected.

K2[Cd(CN)4] = 2 K+ + [Cd(CN)4]2-

[Cd(CN)4]2- = Cd2+ + 4CN-

Cd2 + s2- ~ CdSl (Yellow)

Based on the above mentioned ,behavior i.e. the tendency to ionize or split into
the constituents the complex ions were classified as perfect & imperfect
complexes. In general, the complex formation equation is represented as
follows -

[MLJ
M + xL = MLx. Kstab = - --
[M] [Lt

MLx~ M +xL
 1 [Ml [L]'
Kinst Ab = =
K,1.,11 [ MLJ

denotes the instabili ty constan t of the complex & it gives the measur e of
Kin s tab

stability of the complex w.r.t it's dissocia tion into metal & ligand. If K stah is
very high, then the extent of dissocia tion of complex into its constitu ents is
very small & - such complex es are referred to as perfect complex es.

On the other hand, if kstab is low, then the complex dissocia tes to a signific ant
extent & such complex es are describe d as the imperfe ct complex es. Thus, the
perfect & imperfe ct complex differ only in the degree of stability constan t &
there is no sharp line of demarca tion between them & it is actually a relative
concept to some extent.

Examp le

Suppos e the stability constan ts of the followin g complex es follows the order

It can be conclud ed that perfectn ess increase s in the order

Perfectn ess increas es

f) Some basic definit ions of Coord ination Chemi stry

( 1) Ligand: In Co-ordi nation chemist ry a ligand is a molecul e or ion, carrying .
suitable donor groups capable of binding to a central atom. Strictly speakin g,
a molecul e or ion does not become a ligand until it is bound and prior to that
it is formally called a - proligan d.

e.g.
: NH 3 [Cu(NH 3 ) 4 ] 2+
Proligand
LNH 3 is a ligand
 Coordinati on Chemistry
(2) Coordina tion number:
.
Coordinat ion number of the central metal atom or ion · equal to the number
is .
. h h t
of sites at which the ligands are attached wit t e cen ra 1 metal atom or 10n.

For e.g. -

• Oxalic acid:
COOH ~ 0 =C- o- + 2H+
I I
COOH O = C- o-
Here oxalate ions have two donor sites.

:. (Denticity = 2)

In a complex with Pt 2 +
0 = C- 0 0- C = 0 2-
~ /
= Square planar complex
/Pt'
O=C-0 0-C=O

C .N = number of ligands x denticity of ligands.

So, here CN = 2 x 2 = [Link] y of a ligand refers to the number of donor

sites of one ligand that is bound to the central atom.

(ii) In a complex M (AAA)2, AAA is a tridentate ligand

So, C .N = 2 x 3 = 6

The secret of getting ahead is getting started. The secret of

getting started is breakin g your complex , overwhe lming tasks
into small managea ble tasks, and then starting on the first
one.
Coordination Chemistry IMPOSSIBLE IS NOTHING
(t Classification of ligands:
(A) Ligands

\j/
Having one or more lone pair of
l Based on the nature of a donor electron s
'¥
Having no lone pair but n electron
electrons for (J donation to the clouds, e.g. alkenes, alkynes,
metal centre (e.g. NH 3, OH -, F-, Cl-, benzene, cyclopentadienyl arnon ,
CO , py, R3P, dpy or bpy , en etc) etc

(B) Ligands
Classification based on the nature of
metal - ligand bonding interaction

Only ligand ➔ metal u bonding Both (J (ligand to metal) and n

(metal to ligand or ligand to metal)
(Jbonding (i.e . ligands having no bonding
suitable orbital for n bonding with
the metal centre) e.g. NH3, H2O, en,
edta4 • etc.

With suitable vacant orbitals to With suitable filled orbitals

receive back the electrons from the for n donation to the metal
metal centre (i.e. a donor and n centre (i.e. a donor + n
acceptor) . These are called the n donor). These are called the
acid ligands, e.g. PR3, CN-, CO, bpy, n donor ligands e.g. OH -, F-,
alkenes, benzene, etc. I- etc.

(C) Classification of th·e ligands based on the Number of Donor Sites and
' '

Coordination Behavior: This classification is on the basis of the number of

donor sites (present in a particular ligand) which can participate
(simultaneously in making the metal ligand linkage. The number of such
donor sites determines the denticity of the ligands. The ligands with one
donor site are called the monodentate ligands, the ligands with two such
donor sites which simultaneously participate in making two different metal -
 Coordination Chemistry 1~:•u - d
having such
lioand
0
linkaaes
0
are called the bidentate ligands; the igan s .
donor sites more than two are described as the po1Y en a
. d t te or mult1dentate
.
ligands. The multidentate ligands .
are tndentat~, te t ra d ~n tate , pentadentate
. '
I
hexadentate etc. for the donor sites three, four, five and six respective Y· 1

Ligands
! Based on the denticity of the ligands

Monodentate Multidentate (chelating)

+
l •
Bridging Chelating

(e.g. hydrazine im-, 4, 4'-bpy, etc) l

Symmetrical Unsymmetrical

(e.g. en, ox2 -, etc) (e.g. gly-, oxine, etc)

Note: Monodentate ligands:

A monodentate ligand can occupy only one coordination site in the
coordination sphere of a complex. They generally possess one donor site.
Sometimes, the ligands having more than one donor sites or binding site can
also act as the monodentate ligands. For example, hydrazine (H2N - NH2)
bears two donor sites but these two donor sites cannot be used to occupy two
coordination sites of the coordination sphere of a metal centre. If it acts as a
bidentate chelating ligand, a three membered chelate ring is to be produced .

. 'G'
M ._ N N ---+ M :N+H 2

(im- bri~u" and Zn" in M/ I (Stable)

Superoxide dismutase enzyme) ~N+H 2

(not stable)
Coordin ation Chemist ry IMPOSSIBLE IS NOTHING
N+H
/2
M

(bridging ligand)

Such a straine d three membe red chelate ring is not stable. Moreov er, in
the chelate ring produce d by hydrazi ne, the adjacen t N sites bear the positive
charge in the same coordin ation sphere. This electro static repulsi on creates
an unfavou rable situatio n. This is why, it acts as a monode ntate ligand.
Howeve r, it can act as a bridgin g ligand.

Some represe ntative exampl es of the monode ntate ligands are given 1n the
followin g table.

• Some examp les of the monod entate ligand s

Formul a Name of the Formul a Name of the
(donor site ligand when (donor ligand when
bold) presen t in site presen t in
comple x bold) comple x
Neutral molecu les Anions
H20 aqua F- fluorido
NH3 amm1ne Cl chlorido
CH3NH2 methyla mine Br- bromido
co carbony l 1- iodido
NO nitrosyl OH- h y droxido
cs thiocarb onyl CN- cyanido - C
CsHsN pyridin e (py) Ne- cyanido - N
(i.e. isocvan ido)
PPh3 triphen yl OCN- cyanato - 0
p hosp hine
AsR3 trialkyl arsane NCO- cyanato - N
(i.e. isocvan ido)
(C2Hsb 0 diethyl ether SCN- thiocva nato - S
NF3 nitrogen NCS- thiocya nato - N
trifluori de (i.e.
 Coordination Chemistrv IMPOSSIBLE IS NOTHING
isothiocyanato)
C 2 H4 ethene (ethylene) N02- nitrito - N
CH3NC methylisocyanido ONO- nitrito - 0
Cations H- h ydrido
NO+ nitrosylium N- azido
3
NH2N+H3 hvdrazinium 02- oxido
CH3Coo- acetato
N3- nitrido
NH2- amido
NQ 3 - nitrato
NOS- nitrosylsulfido

~ Bidentate Ligands:
The ligands having two different binding sites suitably oriented to occupy
simultaneously two coordination sites of a metal centre are called the
bidentate ligands. In such cases, chelating rings are formed. The 5 and 6
membered rings are strain-free rings. Thus the 5 and 6 membered rings are
more stable. Between the 5 and 6 membered rings, the 5 membered ring
is more stable.

✓• Polydentate Ligands:
The ligands having more than two binding sites for coordinating
simultaneously in a _coordination sphere of a metal centre are described as
the polydentate or. multidentate ligands. Depending on the number binding
sites (i.e . denticity) the ligands are tridentate, tetradentate , pentadentate,
hexadentate, etc. The examples of such ligands are given in following table.
 IMPOSS lHLE 1:, l'IVlJ-1J J ~V
Coordination Chemistry
• Flexi dent ate Ligan ds
In some cases for polyd entate ligand s (and even for the biden tate ligand s like
o:,...'Yanion s RC0 2 -, CQ 3 2 -, N0 3 - , S0 4 2- etc), all the availa ble bindin g sites of a
partic ular ligand may not partic ipate in makin g the metal ligand linkag e. In
such cases, the dentic ity of the ligand s depen ds on the exper iment al
condi tions. This variab le dentic ity chara cter of the ligand s is referr ed to as the
flexid entate chara cter of the ligand s.

✓• Amb ident ate Ligan ds

The ligand s havin g more than one bindin g site may use differ ent sets of
bindin g sites in differe nt cases, but all the bindin g sites gener ally canno t
opera te simul taneo usly to coord inate a partic ular metal centre . Such ligand s
are descri bed as the ambid entat e ligand s.

The ambid entate ligand s very often produ ce the linka ge isome rs.

In our next lecture we will discuss the

:,
IUPAC Nomenclature of
I
Coordination Com pou nds

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