Advanced Inorganic Chemistry

Chapter 5: ORGANOMETALLIC COMPOUNDS

5.1 DEFINITION:
Metal complex compound with at least one Metal – Carbon
bond.
Example:
[Co(Cp)(CO)2] Cyclopentadienyldicarbonylcobalt(I)
[where: Cp = (C5H5)-]
Exception:
Cyanometalcomplex is Werner complex compound but not
organometalic complex compound. Contrary, its isoelectronic
compound, the carbonylmetal complex is an organometalic
compound.

Seri Kimia Anorganik - I Wayan Karyasa

Advanced Inorganic Chemistry
Chapter 5: ORGANOMETALLIC COMPOUNDS
5.2 Organometallic complex types
Carbonyl - complex

Alkyl - complex

Carbene or Alkylidene - complex

Carbyne or Alkylidyne - complex

Alkene - complex

Alkyne - complex

Allyl - Cyclopentadienyl - Arene - complexes

Seri Kimia Anorganik - I Wayan Karyasa

Advanced Inorganic Chemistry
Chapter 5: ORGANOMETALLIC COMPOUNDS

Seri Kimia Anorganik - I Wayan Karyasa

Advanced Inorganic Chemistry
Chapter 5: ORGANOMETALLIC COMPOUNDS

ηx = Number of Carbon atom which is coordinated to Metal.

μx = Number of Metal atoms which are bridged together.
Seri Kimia Anorganik - I Wayan Karyasa
Advanced Inorganic Chemistry
Chapter 5: ORGANOMETALLIC COMPOUNDS

5.3 MO Bonding Models of Organometallic compounds

MO-Diagram for ML6-Complexes (σ-bonding only)

Seri Kimia Anorganik - I Wayan Karyasa

Advanced Inorganic Chemistry
Chapter 5: ORGANOMETALLIC COMPOUNDS

MO-Diagram for ML6-Complexes (σ-front and back-bonding)

Seri Kimia Anorganik - I Wayan Karyasa
Advanced Inorganic Chemistry
Chapter 5: ORGANOMETALLIC COMPOUNDS

Consequences of MO’s Models consideration

Complexes with -weak donor ligands Complexes with -strong donor ligands

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Advanced Inorganic Chemistry
Chapter 5: ORGANOMETALLIC COMPOUNDS

Complexes with -acceptor ligands Complexes with -donator ligands

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Advanced Inorganic Chemistry
Chapter 5: ORGANOMETALLIC COMPOUNDS

5.4 Symmtries of s-, p-, and d-Orbitals dependent on the Point Groups

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Advanced Inorganic Chemistry
Chapter 5: ORGANOMETALLIC COMPOUNDS

5.5 Isolobal Concept

Definition:
Two fragments are isolobal, if the number, symmetry
properties, non-transferred energy and forms of frontier
orbitals, as well as the number of electrons in the
fragments are similar.

Seri Kimia Anorganik - I Wayan Karyasa

Advanced Inorganic Chemistry
Chapter 5: ORGANOMETALLIC COMPOUNDS
Construction of frontier orbitals on organic fragments of CH4, CH3, CH2, CH
through successive removal of H• => non bonding MOs,

MO
anti-bonding

Frontier
orbitals

MO
bonding

Number of
VE

Seri Kimia Anorganik - I Wayan Karyasa

Advanced Inorganic Chemistry
Chapter 5: ORGANOMETALLIC COMPOUNDS

Frontier orbital forms

Seri Kimia Anorganik - I Wayan Karyasa

Advanced Inorganic Chemistry
Chapter 5: ORGANOMETALLIC COMPOUNDS
Construction of frontier orbitals of organometallic fragments of
ML6, ML5, ML4, ML3
through successive removal of L•+ => non-bonding MOs

MO
anti-bonding

Frontier
orbitals

MO
bonding

Number of VE

Seri Kimia Anorganik - I Wayan Karyasa

Advanced Inorganic Chemistry
Chapter 5: ORGANOMETALLIC COMPOUNDS

Frontier orbital forms

hoped (e)

Seri Kimia Anorganik - I Wayan Karyasa