Metal Carbonyls

Presented by
Ondrila Deb
MSc (Applied Chemistry)
A4450918040
Fig:- Resonance structures of M-CO bond
 LUMO

HOMO

Fig:- Molecular Orbital Diagram of CO

Bonding.
 Here,HOMO of CO holds
loosely bound
electrons,hence donation
of electrons to the central
metal ion takes place,
forming M-CO σ bond.
 LUMO of CO are 2
antibonding,vacant
orbitals,from which one of
these undergo π-overlap
with filled d-orbitals of
metal.
 This is called synergistic
effect, where σ bonding
strengthens π-bonding and
vice versa.
Infrared Spectroscopy of
Carbonyl Complexes
 A clear, sharp and high intensity band is observed for
CO bond but metal - carbon stretching gives low
intensity, diffused and broad bands.
 It is observed that back bonding leads to increase in
metal - carbon bond order and decrease in CO bond
order.
 Hence carbon-oxygen stretching frequency shifts to
lower wave number.
Bond order is directly proportional to bond strength and
inversely proportional to bond length.
 Classification of Metal carbonyls
on the basis of type of bonding.
 Terminal metal carbonyls:-
The molecule has linear skeletal allignment and the ligating carbon of
CO donates 2 electrons to the central atom.

 Doubly bridged metal carbonyls:-

Here, each metal-carbon bond is formed by one electron donated by
the metal and one electron donated by the carbon of CO

 Triply bridged metal carbonyls:-

Here carbon of the bridging group shares one of its electron with an
electron contributed by one metal atom and another of its electrons
with an electron contributed by the second metal atom.The third
metal carbon bond is formed by donation of π-electron pair of CO
to the metal atom.
Examples

Cr(CO)6 Fe2(CO)6 Rh6(CO)16

 Bonding modes in different
types of metal carbonyls
Bonding modes of CO Bond order Range for ʋ(CO) in
(cm-1) neutral complexes (cm-1)

Free carbon monoxide 3 2143

Terminal carbonyl <3 2150-1950
Doubly bridging carbonyl 2 1850-1750
Triply bridging carbonyl <2 1720-1620
 Spectroscopic data for different
types of carbonyls
Complex ʋ(CO) in cm-1

[V(CO)6 ]- 1860

[Cr(CO)6] 2000

[Mn(CO)6]+ 2090
 Synthesis
 Direct Reaction
300K
Ni + 4CO Ni(CO)4
475K
Fe + 5CO 200 atm Fe(CO)5

 Reductive Carbonylation
CrCl3 + Al + 6CO Benzene Cr(CO)6 + AlCl3
925K
OsO4 + 9CO 350 atm Os(CO)5 + 4CO2
 Photolysis
2Fe(CO)5 hʋ Fe2(CO)9 + CO

 Pyrolysis
250K
2Co2(CO)8 Co4(CO)12 + 4 CO
 Reactivity.

 Substitution
Cr(CO)6 + C6H6 [Cr(C6H6)(CO)3] + 3CO
Fe(CO)5 + PPh3 [Fe (PPh3)(CO)4] + CO

 Reductive Decarbonylation
Fe(CO)5 + 4OH- [Fe(CO)4]2- + CO32- + 2H2O
 Oxidative Decarbonylation
Fe(CO)5 + I2 Fe(CO)4I2 + CO

 Disproportionation
3Mn2(CO)10 +12Py 2[Mn(Py)6]2+ + 4[Mn(CO)5]- +
10CO