Coordination Compound/ Complex compounds

→ The compounds in which at least one complex ion is present.

Ligants

Ku [ fe (CN) 6 ] aq 4k+ + [fe (CN)6]-4

↓ Coordination Entity
Counter ion/ spectator
Ion/ outer sphere Central metal ion/atom

→ Double salt

Mixn of 2 salts
In ag soln followed
By crystallization.

K2SO4.Al2(SO4)3.24H2O(Potassium)
↓
ag

2k+ + 4SO42- + 2AI3+

 Werhes Theory

Crcl3(NH3)6 Ag NO2 + 3△ga = 1 : 3

(complex) ↓
White ppt

[ Cr (NH3) ]cl3

Tounter ion

Secondary valiancy

Cr (NH3)5 SO4 Cl Bacl2 white ppt (BaS04)

(Cr (NH3)5 a) SO4 ag SO4 2- + [Cr (NH3)5 a] +2

 Coordination chemistry
 The branch of chemistry that deals with the study of coordination
compounds, their preparation physical and chemical properties etc.

Coordination entity:- its companies of central metal and species

connected by coordination bonds.

Coordination sphere:- the coordination entity is enclosed in a square

bracket which is called coordination sphere

Coordination metal atom :- the metal present inside the sphere

Ligands
The sphere other than central metal (or the species which are e - donor)

D A
↓ ↓
Donor acceptor
↓ ↓
Ligands central metal atomisotion

Ligands

Denticity :- the no. of bonds formed by the ligand with central atom.

→ monodentate or unidentate ligands.

The ligands which can make only one bond.

Eg :- X⊖ N⊖H3 CN⊖ , OH⊖ etc.

→ Bidendate Ligands:- those which can form 2 bonds with

central atom. (2 donor sites)

(en) = Ethylene diamine CH2---- CH2 (Ethane -1,2, diamine)

│ │
N̤H2---- N̤H2

(OX) = C3O4 ⊖
 O = C - O- (Oxalate ion oxalotor)
|
O = C - O-
→ Poly dentate Ligands :- it can form more than 2 bonds
Tetradentate Hexadentate
↓ ↓
EDDA Ethylene diamine
Ethylene diamine tetracetate
diadcetator

o
II
O
O⊖ __ C _ CH2 CH2 __ CH2 II
| | CH 2 – C - O⊖
CH2 __ CH2 O O N N
| | II II CH 2 - C - O⊖
HN̤ HN̤ - CH2 - C - O O - C – CH2
⊖ ⊖
II
O
O
II
CH2 C – O-

Cycle structure forms by bidendate or polydentata ligands

with Central atom.

CH2 __ N̈ H2

| Cr → It increases stability of coordination compds.

CH2 __ N̤ 2
5 – atom Ring
→ 5 and 6 numbered rings are more stable
→ Anuridentate :- the monodendate Ligands which can connect two
different atoms
--
CN̈ (cyanide –c)
N̈ C- (Cyanido -N)
N̈ O2- (Nitrito -N)
 -ONO (Nitrito -N)
-SCN̈ (Thiocyanato-S)
N̈ CS̈ (Thiocyanato - N)

 Flexidentate :- The ligands which can change their Denticity

SO42- , CO32- etc

(1 or 2) (1 or 2)

 Homoleptic Compd. Heteroleptic Compd.

— Only one type of ligands — Two or more types of ligands.

are present

[Cr (NH3)6]3+ [CrCl3 (NH3)2 SO4]

Conxination numbers :- no. of bounds formed by ligands with (NA)

C. N = < (No. of ligands Denticity )

[Cr (fe)2 cl2 ]cl ku [fe (CN)6 ]

C.N = 2 × 2 + 1 × 2= 6 C.N = 1 × 6 = 6
Oxdn state of CNB :- CHARGE C.N.A.

III II

(i) [Cr (en)2 O2 ]O (ii) ku [fe (CN)6]

Z +0 + (-1 ×3)=0 1 × 4 + X + (-1×6) =0
Z=3 X=2

(ii) K3 [Cr (c2a)3] 5d2o

3+ x + (-2 × 3) =0
X=3

 Coordination ________________
→ Beyond by C0 x and hybridization

 Iuffc ______________

CMA (if sphere in –ve) (oxdn state)

 Counter ion name -hydrate
Without number

+
→ K3 [Cr (C2O4)3 ]-

Potassium Trioxalato chremate (III)

→ III [ feCl3 (ON)2 (H2O]3H2O

Iron (III) aquatrichoridodicyano –C ferrate (II) Trihydrate

3 + x - 3 - 2 = 0
X = 2

→ [Cocl4 (NH3)2 ]-

Diaminetetrachlorocobaltate (III) ion

X - 4 = -1
X = 3
→ [Cocl (NO2) (NC)(CH2O)3 ]
Triaquachloridocyano –N- nitro –N- cobalt (III)
  Formula from IUPAC nomendature

(1) Tetraanineaqua chloridocobalt (III) chloride

[ Co (NH3) (H20) cl ]cl2

3+ + (-1) + (-x) = 0
X=2

(2) Dichloridobis (ethane -1, 2 ________)Ab (III)

[ Cocl2 (en3)2]2

3+ + (-20) = +1

 Isomerism
equal molecular unit
The species craving same molecular formula but different structure
Or spatial arrangement of atom or group

Structural isomers
2 Types
Stereoisomers

Structural Isomers (Mf same but different structures)

(1) Linked isomers :- MF same but linking atom different

→ possible only when ambient Ligand is present

[Crcl3(NH3)3] X

[Cr(CN)2Cl(NH3)3] = [Cr(NC)2Cl(NH3)3]

(2) Hydrate Isomerism (solvate isomers)

→ Different in the no. of water molecules in erystallim salt

 [Cr(H2o)3cl3] H2O

[Cr(H2o)4cl1] cl

(3) Ionization isomers HF same but when compass are disowned into
H2O, the different ions are liberated.

[Crcl2(NH3)2 (H2O)2] + = cl- H2O

[Crcl(NH3)2 (H2O)3] 2+ Cl-2

[Co(SO4) (NH3)4 cl] Cl-

[Co(NH3)4 cl2] 2+ SO4-

 Coordination Isomers

[Co(NH3)6 6] + [Crcl6]-

[Co(NH3)6 6] + [Crcl6]-

When there is a change in the +ve and –ve spheres in the coordination
complex containing 2 spheres.

Stereoisomers

→ MF same but different spatial arrangement of Ligands

cl Br Br cl
Cr Cr
cl Br cl Br

Cis Trans

Two types :-
(1) Geometrical isomerism :- MF same but geometrical arrangement
different.
(2) Optical isomers :- MF same but optical activity different
 Geometrical Isomers

(1) Tetrahedral (2) Square planner (3) Trigonal Bipyramidal

(4) Octahedral

(1) Tetrahedral
→ It appears identical through all planes because of (109.28.) angle.
So rotation is free. But in SP, and octahedral have 900 angle so, it is
not rotation free.

C.N =4
[MA2B2] M = Central metals
A and B are monodentate Ligands

A B A A
M M
B A B B

Trans Cis

B. P → Depends upon forces and mass and size (surface area)

M.P→ mass, symmetry

[MA2BC]

A B A C
M m
A C B A

Cis Trans

[MABCD] A = highest mol. mass

D = lowest mol. mass
A>B>C>D

A C A C
M M
 D B B A

Trans Cis

[MA3B]

A A A B
X M M
A B A A

Both are Identical

 Octahedral

C.N = 6
[MA2B4]

A B
A A A B
M M
A B A A
A B
Trans Cis

→ [MA3B3]

A B
B A A B
M M
B B A B
A A
Meridional (mer) facial (fac)

Square Planer

→ [M(AA)B2] X
 AA M

→ [ M(AA)(BB)] X

AA M AA

Octahedral

→ [M(AA)2B3 ]

AA B
B
M AA M AA
B
AA B
Cis Trans

→ [M(AA)3] X

AA AA
M

AA

 Optical Isomers (Enantiomers)

(i) PP1,
 d λ loevbrolating
(-)
deoxtrodation (lgt)
(+)
(right)

________
________
________
______ ag. soln

Symmetrically → Optically inactive

Chiral (asymmetrical ) → Optically active

→ [M(AA)2B2 ]
AA
B
B AA
M M
B
B AA
AA

AA AA
M X

 VBT (valence Bond Theory) : Hybridization

Coordination no. Hybrid Geometry

3
4 sp Tetrahedral (109.280)
dsp2 square planer (900)
 5 sp3d Trigonal bipyramidal

dsp3x

6 sp3d2 octanedral

d2sp3

d=

degenerate orbital
→ CFT / CFST

L
X Y
Octahedral complex

L L
L
. Y

dxy ; dyz, dxz=

dx2 – y2 = x

(2 x .6 = 1.2)

↕ 3/5 + 0.6 0.
△0 – Bary centre
↕ 2/5= 00-4△0
 +2g → Triply
regenerated second level

(3 x 0.4) = -1.2

t2g < eg as per auffbau principle. t2g in filled first

109.28’

t2g 0.4 x 3=3.2

↕ 2/5.
△t
↕ 3/5

0.6x2= -1.2

 Strong field Ligands

C – N donor species are always strong field ligands

→ They form low spin complex → pairing of Ligands is done.

[Cr (CN)6]3- K3 [Cr (CN)6]

24 Cr = [Ar] 3d54s2

X + (-1 x 6) = - 3 3+ X + (-1 x 6) = 0

X= 3

Cr+3 = 4s0 3d3 4p0 4d0

C.N = 1 x 6 = 6

CN is strong field ligand so form low spin complex

3d3

7 7 7
 d2sp3

˥Ꙇ ˥Ꙇ ˥Ꙇ ˥Ꙇ ˥Ꙇ ˥Ꙇ
- - -
CN CN CN -CN -CN -CN

CN -3

CN CN

K3 G

CN CN

CN

 CFT

d – orbital occupancy

(i) △0 > P

→ CFSE → Crystal filled splitting energy

→ pairing is done in t2g set of orbitals if required

→ △0 > P in presence of SFL

→ SFL = strong field Ligand.

(2) △0 < P ( in presence of weak filled ligand

→ Pairing is not done.

SFL WFL

d1 t2g1 eg0 t2g1 eg

d2 t2g2 eg0 t 2g 2

d3 t2g3 eg0 t 2g 3

d4 t2g4 eg0 t2g3eg2

 d5 t2g5 eg0 t2g3eg2

d6 t2g6 eg0 t2g4eg2

d7 t2g6 eg1 t2g5eg2

d8 t2g6 eg2 t2g6eg2

d9 t2g6 eg3 t2g6eg3

d10 t2g6 eg4 t2g6eg4

 Bonding in metal carbonyl

CO, -CN, = ∏ - acids

CO → Synergic Bond

∏*

2∏
M :C O
6 Bond o

→ In metal carbonyl synergic bond in formed : synergic bond is a comb n o

- bond by carbonyl group in the react d- orbital of metals and II – bonds
of filled orbitals of metals with vacant orbital (∏*) of carbonyls

→ Stability of metal carbonyl is very high due to form n of synergic bond

[Ni (co)4]

Ni = 3d8 4s2 4p0

˥Ꙇ ˥Ꙇ ˥Ꙇ ˥ ˥ ˥Ꙇ

˥Ꙇ ˥Ꙇ ˥Ꙇ ˥Ꙇ ˥Ꙇ
 Co Co Co Co

˥Ꙇ ˥Ꙇ ˥Ꙇ ˥Ꙇ ˥Ꙇ ˥Ꙇ

Bond

Col (l) co (g) △iH1 + △iH2 co+2

 △
= +ve

CuSO4, (△) Cu2 SO4 (white) + 5H2O ↑

△

5H2O

 Cr+3 → stable only in octahedral complex because of t2g+

configuration.

 Fe+2 stable in octahedral complex due to t2g+

 Co+2 is stable in ag soln due to its higher hydration energy which can
compensate the sum of atomization and ionization enthalpies.

 Co+3 t2g+

 Ni+2

 Co+1 stable in dry state (anhydrous from) only due to d10

E˚M2+/m values = SRP value

 If SRP is +ve, the metal can displace H from acid or base and form m +2
ion.

 +ve, can’t displace, can’t from

Cu + Ha X Cu+2 Zn + Hcl Zna2 + H2 ↑

E˚ w+2/cu = 0.34 V E˚ zn /zn = 0.76 v-
+2

→ The lower is the SRP, the higher is the reactivity, its above example
cu is more reactive
than Ag

→ The higher is the mobility of ion, the lower is the E o values (usually –
ve)

Eo m+3/ m+2
 E˚ fe+2/fe = -0.44 V
E˚ fe+3/fe +2 = 0.77 V

Q :- Why E˚ ai/ cu is +ve?

It is very higher hydration energy of cu+2 ion due to which its mobility
decreases and Eo
Value becomes +ve
→ Aalthough E˚ fe+3/fe = +ve, is stable because its acquires d5
configuration.

Q :- fecl3 when kept in acid soln , it become fea2 why?

Ans- f˚ fe+2/fe is –ve ; fe+2 ion is more stable in acid soln

 Stability of higher oxidation state

→ O and F can stabilize higher oxdn state (K2G+6O2, Kmn+7O4) because

these 2 elements are highly electro negative.

→ Oxygen is more efficient to oxidise metals to higher oxdn state than f

because O can form
dΠ - PΠ bond.
f

f f o o
T2o Mn 109.281( Mn
f f o
o
f
f

 Magnetic character → Electronic concept

(1) Paramagnetic Diamagnetic

 Unpaired e- * Paired unpaired e-
 Attracted weakly * Repelled weakly in
In magnetic field magnetic field

H = magnetic
 moment
√ n(n+ 2)BM
n = no. of unpaired e-

eg:- Cr > Cr+2

↓ ↓
3d54s1 3d4

n= 6 n=4

H= √ 6(8) H = 4.7

= 6.7

→ Cr+2 = Mn+3
↓ ↓
3d4 3d4

→ H = 4.7 H=4.7

Q:- Cr+2 and Mn+3 both same d4 configuration (and magnetic moment)
but Cr+2 →reducing, mn+3
Is oxidizing why?

Ans:- → Cr+2 → Cr+3 + e-

→ mn+3 +e- → mn+2

→ Cr+6 → d0 + dia

→ mn+7 → d0 + dia

→ zn+2 → dia

Q:- Cr+2 Cu+2 + cu (ag .SO1n) why ?

Ans:- Cu+1 → Cu+2 + e-

Cu+1 +e- → Cu

Because cu+2 has higher hydration energy than Cr+1

Q:- +4
 MnO2 disproportionates why ?

Ans:- because Mn+4 lies b/w oxidation state of mn = +2 +O +7.

 Colour of Transition metals

→ unpaired e- → d-d transition

B
v G
t2g → eg

Maushell

Colour

whell
R y

→ The unpaired e- d-d transition by absorbing the colour of visible region

and complementary colour is observed

 Sc → Sc+3 → X
 mn → mn+3 → mn+7
(exception)
(kmno4)
 Cr → Cr → Cr+4 → Cr+6
+3

(K2G2O7)
(exception)

→ change Transfer (Resonance)

o
⃝ ‖
mn
mn o o-

o o o
o

Kmno4 ia colour ed due to momentarily charge transfer to mm (central atom)

(due to resonance)
 o o

o Cr ----- Ӧ̤ Cr o

o- o-

 Catalytic Properties

holes

It is due to variable oxdn s state and large surface of Transition metals

and their compounds.

Intestinal Compounds

When smaller atoms like H, N C etc are trapped inside host (or
interstices). The new
compounds formed are c/d interstitial compounds.

 Alloy formation (substitution compounds).

→ transition metals form alloy, because they have very less difference
in sizes or similar in
sizes so, they can be substituted at place of one another.

 Oxyanions

Cr0 O72- and mno4

(Dichromate ion) (Permagnet ion)

K2Cr2O7
Commercial (industrial preparation)

(sodium
dichromate)
Chromite are feo.Cr2o3 Nd2Co3 Nd2Cra1 H2SO4 Na2
Cr2O7
O2/△ (acid ify)

feCrO4 iron Black (Roasting) (yellow sodium chromate)

 (potassium Dichromate0
(oxidising agent)
K2Cr2O7 kcl Not a primary
(yellow) reagent
Orange ↓
because hygroxepic nature
Cr0 O72- + fe+2 +3
Cr +fe +3

+H+
Acid medium H-H+ O = H2O Basic medium
H= OH-
(i) Add H2O to the side having less no. of O- (i) Add H2O to the side
having more O and
A term and add double H+ to the opposite add double OH- to the
opposite side
Sides.

(ii) If H remains unbalanced add H+ do the (ii) If H remain

unbalanced add OH- to the
Side having less H. side having more H
and same no. of H2O
to the opposite side.

 Charge balancing

-ve charge less + e-

+ve charge more + e-

Cr2 O72- + fe+2 Cr+3 +fe+3

Cr2 O72- + 14H++6e- 2Cr+3 + 7H2O

fe+2 fe+3 + e-
Cr2 O72- + 14H+ + 6e- 2Cr+3 + 7H2O

6fe+2 6 fe+3 + 6e-

Cr2 O72- + 6fe+2 14H+ 2Cr+3 + 6fe+3 + 7H2O
→ MeO2 KOH k2 mno4 electrolysis kmnoH
↓ ↓
Magnate Potassium Potassium
Ore Mangnate per mangnate

I – block elements → Inner Transition metals 3rd group metals.

 Uf – Lanthanoid → Belong to Lanthanoid group → 38-81

Sf – Actinoid series → belongs to actinium group → 89-103

Lanthanoid contraction → The size of Lanthanoid decreased along

the series in a regular
pattern.

→ Oxidation state
(n-2) f 1-14 (n-a)d0-1 ns2

Ce +4 → In this case it has noble gas configuration stable

Common oxidn state → +2 and +3 because ‘f’ orbital gas very poor
shielding.