Lecture 23;

CH 410:
Chemistry of p-Block and d-Block
Elements

Dr. Akshai Kumar A. S

Department of Chemistry
&
Centre For Nanotechnology
Indian Institute of Technology Guwahati
Guwahati – 781039, Assam, India

CH 410 Chemistry of p-block and d-block

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Dr. Akshai Kumar
Crystal Field Theory –

² Gross over simplification and qualitative

² d4,5,6,7 can be either high or low spin

² High-field ligands gives low-spin complexes

² Does not explain why certain ligands have a

strong/weak ligand field

² Splitting of d-orbitals is considered as a “fact”

CH 410 Chemistry of p-block and d-block
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² Why is W(NH3)6 is not a stable compound?

² Why is W(CO)6 is very air stable and unreactive?

² Why is W(PMe3)6 is very air-sensitive and reactive?

² Why d0 systems such as Ti4+ cannot for stable

carbonyl complexes?

² Is there a model that gives accurate electronic

structure calculations?

CH 410 Chemistry of p-block and d-block

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Dr. Akshai Kumar
Ligand Field

² Conventional Molecular Orbital (MO) Theory

Bonding
H2 : 1⁄√2 + 1⁄√2 σ
σ*

1s 1s

σ 1⁄√2 + 1⁄√2 σ*

Anti-bonding
CH 410 Chemistry of p-block and d-block
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Dr. Akshai Kumar
Ligand Field

² One s, three p and five d-orbitals of the isolated

ion is taken into consideration

² 6 pure σ-donor ligands(NH3) – 6 lone pair orbitals

(6 ligand group atomic orbitals - LGAO)

² Octahedral case;
One s, three p and two dσ (dspσ) have right
symmetry to interact with 6 LGAO’s

CH 410 Chemistry of p-block and d-block

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Dr. Akshai Kumar
 M-L σ* bonds
Ant-bonding

Non-bonding

M-L σ bonds
Bonding

CH 410 Chemistry of p-block and d-block

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Dr. Akshai Kumar
For pure σ-donating ligands dπ of CFT is non-bonding
in MO

Similarly, dσ of CFT is M-L σ anti-bonding in MO

d6 complex; 6e from metal, 12 e from ligand

18 e occupy the levels up to dπ

Splitting increases with increase in strength of

M-L σ-bond

High-field σ-donating ligands form strong σ-bonds

CH 410 Chemistry of p-block and d-block
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Dr. Akshai Kumar
As most bonding
(and therefore
“chemistry”)
occurs in the
valence (or
“frontier”) orbitals
of a compound,
most reactions of LUMO
metal complexes
occur at the metal
centre. Non-bonding / Frontier
HOMO

L(σ) always lies below M(dσ)

More L character
CH 410 Chemistry of p-block and d-block
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CH 410 Chemistry of p-block and d-block
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How about ligands that also have π-acceptors? CO?

Bonding in Metal Carbonyls

Valence bond structure of CO; C O

(formally, a carbanion)
Vague explanation of M-CO
M C O bonding. Does not describe
why transition metals form much stronger bonds
with CO than main group metals

CH 410 Chemistry of p-block and d-block

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Dr. Akshai Kumar
 H3B C O 23 kcal/mol

(CO)5W C O 42.5 kcal/mol

(PR3)2ClIr C O > 70 kcal/mol

π π*

C O C O

CH 410 Chemistry of p-block and d-block

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Dr. Akshai Kumar
Bonding in Metal Carbonyls

σ bond (Using the metal

s, pz and dz2 orbitals)

M C O Z

dπ-pπ* back bond

CH 410 Chemistry of p-block and d-block

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Metal-Ligand π-bonding
t2g π*

eg σ* eg σ*

M-L σ-bonding
t2g non-bonding

t2g π

M CH 410 Chemistry of p-block and d-block

L
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Dr. Akshai Kumar
 Oh with π-acceptor Ligands
t1u*

Empty Ligand π-orbitals

a1g*
eg* (dx2-y2, z2)

Δο With no back bonding

t2g Δο With back bonding

(dxz, yz, xy)

Metal Orbitals

Ligand
eg σ orbitals
a1g
t1u CH 410 Chemistry of p-block and d-block
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Dr. Akshai Kumar
MO Diagram: Oh Oh with σ -donor Ligands
t1u*

a1g*

eg* (dx2-y2, z2)

t2g

Metal Orbitals (dxz, yz, xy)

Ligand
eg σ orbitals
a1g
CH 410 Chemistry of p-block and d-block
t1u Dr. Akshai Kumar
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MO Diagram: Oh Oh with σ -donor Ligands
t1u*

a1g*

eg* (dx2-y2, z2)

t2g

Metal Orbitals (dxz, yz, xy)

Ligand
eg σ orbitals
a1g
t1u CH 410 Chemistry of p-block and d-block 16
Dr. Akshai Kumar
MO Diagram: Oh Oh with σ -donor Ligands
t1u*

a1g*

eg* (dx2-y2, z2)

t2g

Metal Orbitals (dxz, yz, xy)

Ligand
eg σ orbitals
a1g
CH 410 Chemistry of p-block and d-block
t1u Dr. Akshai Kumar
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MO Diagram: Oh Oh with σ -donor Ligands
t1u*

a1g*

eg* (dx2-y2, z2)

t2g

Metal Orbitals (dxz, yz, xy)

Ligand
eg σ orbitals
a1g
CH 410 Chemistry of p-block and d-block
t1u Dr. Akshai Kumar
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 Oh with π-acceptor Ligands
t1u* t2g *

Empty Ligand π-orbitals

a1g*
eg* (dx2-y2, z2)

Δο With no back bonding

t2g Δο With back bonding

(dxz, yz, xy)

Metal Orbitals t2g

Ligand
eg σ orbitals
a1g
t1u CH 410 Chemistry of p-block and d-block
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Dr. Akshai Kumar
 Oh with π-donor Ligands
t1u*

a1g*
eg* (dx2-y2, z2)
Δο
Δο t2g *
t2g
Filled Ligand π-orbitals
(dxz, yz, xy)
Metal Orbitals t2g

Ligand
eg σ orbitals
a1g
t1u CH 410 Chemistry of p-block and d-block
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Dr. Akshai Kumar