COORDINATION

COMPOUNDS
isomerism theories
basics &
nomenclature
 COORDINATION
COMPOUNDS
isomerism theories
basics &
nomenclature
 COORDINATION
COMPOUNDS

Valence Bond Werner’s Crystal Field

Thory Theory Theory
 WERNER’S THEORY
Valencies

primary valency secondary valency

SIMPLY CONCISE
ionisable non ionisable
non directional directional
satisfied by satisfied by
anions ligands
OS of the metal CN of the metal

[Cr(H₂O)₆]Cl₃
 VALENCE BOND THEORY
1) metal - ligand bond arises when a filled ligand orbital overlaps a
vacant hybrid orbital of metal.
2) central metal atom provides requisite no. of vacant orbitals of
same energy, for that they hybridize their (n-1)d, ns, np, nd orbitals.

CN SIMPLY CONCISE
hybridisation geometry 3) strong field ligands like NH3,
CN-, CO force pairing of electrons.
4 sp³ tetrahedral

4 dsp² sq. planar

5 sp³d tri. bipyramidal

outer orbital complex
6 sp³d² octahedral or high spin complex
inner orbital complex
6 d²sp³ octahedral
or low spin complex
 VALENCE BOND THEORY
+3 +3
[Co(NH₃)₆]³⁺ [Cr(NH₃)₆]³⁺
Co : 4s²3d⁷ Cr : 4s¹3d⁵
Co⁺³ : 4s⁰3d⁶ Cr⁺³ : 4s⁰3d³
3d
SIMPLY CONCISE
4s 4p 3d 4s 4p

d²sp³ (inner d) d²sp³ (inner d)

octahedral octahedral
low spin complex high spin complex
diamagnetic paramagnetic
colourless colourled
 CRYSTAL FIELD THEORY
1) metal - ligand bond is purely ionic and arises from electrostatic
interactions between the metal ion and the ligand.
2) anionic ligands -> point -ve charge neutral ligands -> dipoles
3) in an isolated gaseous metal atom, the d orbitals are degenerate,

SIMPLY CONCISE
and the degeneracy is maintained in a spherically symmetric field
4) the degeneracy of the d orbitals splits in ligand field and the
pattern of splitting depends upon the nature of the crystal field.
 CRYSTAL FIELD THEORY
a) splitting of d orbitals in octahedral field:

dz² dx²-y²
eg

barycentre
SIMPLY CONCISE 3/5Δₒ

Δₒ

2/5Δₒ

t₂g
dxy dyz dzx
 CRYSTAL FIELD THEORY
a) splitting of d orbitals in tetrahedral field:
Δₜ = 4/9 Δₒ

dxy dyz dzx

barycentre
SIMPLY CONCISE t₂

2/5Δₜ
Δₜ

3/5Δₜ

e
dz² dx²-y²
 CRYSTAL FIELD THEORY
Factors affecting CFSE:
1) Oxidation state of metal
OS ∝CFSE
2) nature of metal

SIMPLY CONCISE
3d > 4d > 5d
3) number of ligands
∝
no. of ligands  CFSE
4) nature of ligands

I⁻ Br⁻ SCN⁻ Cl⁻ S²⁻ F⁻ OH⁻ ox²⁻

H₂O NSC⁻ edta⁴⁻ NH₃ en CN⁻ CO

 CRYSTAL FIELD THEORY
Filling of electrons in splitted d orbital:
a) Δₒ P b) Δₒ P

eg eg

SIMPLY CONCISE
d³ d³

t₂g t₂g
 CRYSTAL FIELD THEORY
Filling of electrons in splitted d orbital:
a) Δₒ P b) Δₒ P

eg eg

SIMPLY CONCISE
d⁴ d⁴

t₂g t₂g
 CRYSTAL FIELD THEORY
Filling of electrons in splitted d orbital:
a) Δₒ P b) Δₒ P

eg eg

SIMPLY CONCISE
d⁵ d⁵

t₂g t₂g
 CRYSTAL FIELD THEORY
Filling of electrons in splitted d orbital:
a) Δₒ P b) Δₒ P

eg eg

SIMPLY CONCISE
d⁶ d⁶

t₂g t₂g
 CRYSTAL FIELD THEORY
Filling of electrons in splitted d orbital:
a) Δₒ P b) Δₒ P

eg eg

SIMPLY CONCISE
d⁷ d⁷

t₂g t₂g
 CRYSTAL FIELD THEORY
Filling of electrons in splitted d orbital:
a) Δₒ P b) Δₒ P

eg eg

SIMPLY CONCISE
d⁸ d⁸

t₂g t₂g
 CRYSTAL FIELD THEORY
Filling of electrons in splitted d orbital:
a) Δₒ P b) Δₒ P

eg eg

SIMPLY CONCISE
d⁹ d⁹

t₂g t₂g
 CRYSTAL FIELD THEORY
Filling of electrons in splitted d orbital:
a) Δₒ P b) Δₒ P

eg eg

SIMPLY CONCISE
d¹ᵒ d¹ᵒ

t₂g t₂g
 JAHN TELLER DISTORTIONS
distortions in octahedral geometry which decreases sym. & energy
Reason: unsymmetric filling of eg and t2g orbitals

a JTD is absent in symmetric

a a octahedral field

SIMPLY CONCISE
M
half filed d³, d⁵ (WFL)
a a
full filed d⁶ (SFL) , d¹ᵒ
a
a both d⁸
a
a a a a
M M
a a a a
a
a
when extra eg e⁻ when extra eg e⁻
is in dz² orbital is in dx²-y² orbital
BONDING IN METAL CARBONYLS
CO CO CO CO
CO CO
OC
Ni Fe CO OC Mn Mn CO
OC CO OC OC OC
CO CO CO CO

SIMPLY CONCISE
O
CO CO
OC C CO
OC CO
OC Co Co CO Co Co
OC CO
OC C CO
CO CO
O
BONDING IN METAL CARBONYLS
metal-carbon bond in metal carbonyls possess both σ and π character.

Π Π Π* M - C σ bond : donation of lp of
carbonyl C to the vacant d orbital
M - C π bond : donation of e⁻ pair

SIMPLY CONCISE
σ O
M C from a filled d orbitals of M into the
vacant antibonding orbital of CO
Π
Synergic Bonding
M - C bond strengthens
C - O bond weakens

∝ charge density on metal

IMPORTANCE OF COORDINATION COMPOUNDS
1) significance in biological systems:
a) chlorophyll - complex of Mg
b) haemoglobin - complex of Fe
c) vitamin B12 - complex of Co

SIMPLY CONCISE
2) significance in medicinal chemistry:
a) cis platin - anti cancer agent
b) edta - lead poisoning

3) extraction processes of metals like silver and gold

4) wilkinson catalyst - hydrogenation of alkene