Learning Agenda

B.Tech. Chemistry (CY1L001)

Date: 21/04/2023
What can be used to cut diamond?

What are the bond orders of superoxide and peroxide?

How are pure transition metals generated?

Inner orbital or outer orbital complex?

Image: google
Bonding in Transition Metal Complex

• Werner Coordination Theory

• 18 Electron Rule

• Valence Bond Theory

• Crystal Field Theory

• Molecular Orbital Theory

 Werner Coordination Theory
Two types of valency:
1. Primary or non-directional valency
(number of charge)
2. Secondary or directional valency
(number of ligand)
 Werner Coordination Theory

[CoIII(NH3)6]Cl3 [CoIII(NH3)5Cl]Cl2

[CoIII(NH3)6]Cl3 + 3AgNO3 [CoIII(NH3)6](NO3)3 + 3AgCl↓

[CoIII(NH3)5Cl]Cl2 + 2AgNO3 [CoIII(NH3)5Cl](NO3)2 + 2AgCl↓

[CoIII(NH3)5Cl](NO3)2 + H2SO4 [CoIII(NH3)5OSO3H](NO3)2 + HCl

AgNO3
AgCl↓
 18 Electron Rules
(based on Effective Atomic Number Rule: Sidgwick)

Valid for: (i) electron rich transition metals

(ii) good π-accepting ligands

Metal electrons + electrons from ligands = 18

Ni(CO)4 : 4s23d8 + 4 lone pairs = 18

Used to isolate
Fe(CO)5 : 4s23d6 + 5 lone pairs = 18 purest form of
metals
Cr(CO)6 : 4s23d4 + 6 lone pairs = 18

Ni CO Ni(CO)4 heat Ni
 18 e Rule: How to Count?
η indicates the heptacity or the connectivity of the central metal
with atoms in ligand
μ indicates the bridging ligand connected with how many metals

3-allyl
µ2-chloro

5-Cp Di-μ2-chlorobis[(η3-allyl)palladium(II)]
 18 e Rule: How to Count?
Oxidation state Oxidation state
Ligand Electron Formal Ligand Electron Formal
donated charge donated charge
Carbonyl (M-CO) 2 0 μ-CO (M–(CO)–M) 2 0
Hydrogen (M–H) 2 -1 μ-H (M–H–M) 2 -1
Alkyl (M–R) 2 -1 μ-alkyl (M–R–M) 2 -1
Alkoxide (M–OR) 2 -1 μ-alkoxide (M–(OR)–M) 4 -1
Phosphine (M–PR3) 2 0 μ-phosphido (M–(PR2)–M) 4 -1
Halogen (M–X) 2 -1 μ-X (M–X–M) 4 -1
η2-alkene (sidewise) 2 0 η6-benzene 6 0
η1-allyl 2 -1 η3-allyl 4 -1
η1-cyclopentadienyl 2 -1 η5-cyclopentadienyl 6 -1
Amine (M–NR3) 2 0 Carbene (M=CR2) 4 -2
 18 e Rule: Example

Ferrocene

Fe2+ (3d6): 6
2 x Cp− : 2 x 6 = 12
18
 Metal Metal Bonds

Number of M−M bonds = (n x 18 – Y)/2

n = number of metal centers presents in the molecule

Y = total number of valence electron present in the molecule

Co2(CO)8 : Dimer of Co(CO)4

2 x Co0 (3d9): 2 x 9 = 18
8 x CO : 8 x 2 = 16
34

Number of M−M bonds = (2 x 18 − 34)/2 = 1

 Metal Metal Bonds

[5-CpMo(CO)2]2

2 x Mo+1 (4d5): 2 x 5 = 10
2 x Cp− : 2 x 6 = 12
4 x CO :4x2= 8
30

Number of M−M bonds = (2 x 18 − 30)/2 = 3

 18 e Rule
Application:
• Stability of metal complex, catalysis

Limitation:
• Not general, useful for low oxidation states
 Problems

Metal metal bonds: Os3(CO)12 Ir4(CO)12

Predict M (4d metal)

 Valence Bond Theory
Metal: Lewis Acid Ligand: Lewis Base

• Overlap of filled ligand orbitals and

empty metal orbitals to give
coordinate covalent bond
• Hybridization of metal orbitals
determines the geometry Linus Carl Pauling
(1901-1994)
Hybridization Schemes (VBT)

Coordination
Arrangement Hybridization
Number

4 Tetrahedral sp3 (4s, 4px, 4py, 4pz)

4 Square planer dsp2 (3dx2- y2, 4s, 4px, 4py)

Octahedral d2sp3 (3dx2- y2, 3dz2 ,4s,

6
(inner orbital) 4px, 4py, 4pz)
Octahedral sp3d2 (4s, 4px, 4py, 4pz,
6
(outer orbital) 4dx2- y2, 4dz2)
 VBT Approach for Metal Complexes

[Cr(NH3)6]3+ : Octahedral

[Zn(OH)4]2- : Tetrahedral
 VBT Approach for Metal Complexes

[Ni(CN)4]2- : Square Planer

• Predict the bonding and geometry of [NiCl4]2-

• Predict the bonding and hydridization of [CoF6]3-
and [Co(NH3)6]3+