Chapter PART B METAL CARBNYLS AND

RELATED DERIVATIVES

OBJECTIVES. In Part B of this Chapter, we consider

metal Carbonyls and related derivatives

INTRODUCTION
An organometallic complex is one in which there is direct
metal–carbon bond . This definition is extended to include even those compounds
where the carbon is co-ordinated to a metalloid eg arsenic or germanium or even a
typical non-metals such as boron or silicon. Organometallics can are carbonyls
are formed principally by d- block elements . There, of course some
exceptions.The formation of a carbonyl derivative by BH3 is indeed a very
unusual case
METAL CARBONYLS.

Introduction . Metal Co-ordination complexes in which the sole

ligand is carbon monoxide are called metal carbonyls . We note that
metal carbonyls are usually formed by d-block elements. The first
ever metal carbonyl to be prepared was nickel carbonyl, Ni(CO)4.
This is readily formed when elemental nickel gets in contact with
carbon monoxide even at ordinary conditions of temperature and
pressure.

Ni+ 4CO RT 1atm

Ni(CO)4

All the other carbonyls are prepared using more drastic reaction
conditions .
We note at this point that the majority of carbonyl complexes contain
a transition element as the central atom or, in case of cluster
complexes, the cluster contains transition elements There is however,
a known example of a complex, in which the carbon monoxide is not
co-ordinated to a transition element. This is the boron complex,
obtained when diborane, B2H6 , reacts with carbon monoxide under
pressure to form co-ordination complex in which the central atom is
not a transition element .
 200oC, 20atm H3 B CO
B2H6+ 2CO

All other known metal carbonyls are transition metal complexes. The
methods of preparation vary widely from element to element . As a
general principal, one can reasonably assume that the reaction takes
place between carbon monoxide and a a d-block element under
reducing conditions. Usually high pressure and sometimes high
temperature are required. We illustrate this by considering a few
examples .
For example, there are some carbonyls that are prepared by a
reaction of the metal in with carbon monoxide under very high
pressure
For example, iron reacts with carbon monoxide only when heated to
a temperature of over 200oC, under carbon monoxide pressure of
200atmospheres and above.
Thus , Fe+5CO ,(200oC, 200bars) → Fe(CO)5 .

Molybdenum hexacarbonyl Mo(CO)6, can also be made by a direct

reaction between the metal and carbon monoxide but again in this
case, the reaction mixture must be heated to a temperature of 200oC,
under a pressure of 250-atmospheres and above .

Mo+6CO ,(200oC, 250bars) → Mo(CO)6 .

More commonly, metal carbonyls are prepared by reduction of a

suitable compound in the presence carbon monoxide. Hydrogen, the
alkali metals , the alkali earth metals and aluminium alkyls are
common reducing agents. Sometimes, carbon monoxide itself acts as
a reducing agent .

120atm
2CoCO3+ 8CO+2H2 200oC Co2(CO)8+ 2CO2 + 2H2O
Metal Carbonyls
2MX5+ Na +diglyme CoCO3+2H2+8CO (100-150oC, 100-150bars)
→ 2CM(CO)6 (M=Mo, W , X=Cl, Br)

Chromium hexacarbonyl is prepared similarly but using the

trihalides CrX3

We note here that the reducing agents used vary very widely.
Thus, instead of using sodium metal to reduce chromium trihalides ,
hydrogen, tin, magnesium , zinc , aluminium or Grignard’s Reagents
have been used. In preparations

E.g CrCl3+ Al+6CO (150oC, 300-350bars)+ AlCl3 → 2Cr(CO)6

C 6H6

The very unstable vanadium hexacarbonyl, V(CO)6, has been

prepared by reducing VCl3 , with sodium metal in the polyether,
diglyme,
C6H14O3. = CH3OCH2 CH2OCH2 CH2OCH3

VCl3+4Na C+6CO + 2 C6H14O3 → Na(C6H14O3)2][ V[CO}6]

2Na(C6H14O3)2][ V[CO}6] +2HCl → 2V(CO)6+ H2+ 4

C6H14O3+2HCl

Table 7.1 lists some metal carbonyls

V(CO)6 Cr(CO)6, Mn2(CO)1 Fe(CO)5 Co2(CO)8 Ni(CO)

, dec100oC 0 dec51,oC dec51,oC 4
mpt,154 Fe2(CO)9 (-19.3,,
o
C, dec100,o Co4(CO)1 42.3oC)
C 2
Fe3(CO)12 Co6(CO)1
mpt, 6
140,oC
 Mo(CO)6, Tc2(CO)10 Ru(CO)5 Rh2(CO)8
mpt,148 oC, Tc3(CO)12
bpt,155 oC Ru2(CO)9 Rh4(CO)1
dec Ru3(CO)1 2
2 Rh6(CO)1
6

W(CO)6, Re2(CO)10 Os(CO)5 Ir2(CO)8

o
mpt,170 C,de Ir4(CO)12
c Os2(CO)9 Ir6(CO)16
Os3(CO)1
2

BONDING IN METAL CARBONYLS

Metal Carbonyls are non-classical compounds in the sense that

the bonding mechanism cannot be accounted for in terms of ionic
bonds in the case of substances such as sodium chloride , or in terms
of covalent bonding as is the case in substances such as methane..
Bonding in metal carbonyls is explained fairly satisfactorily by taking
the following points into account.:-
(a) The d-orbitals of some d-block-elements are low energy and of
same order as the energy of the p* on the molecule. CO.Hence,
when these are brought close enough under the right conditions(i.e
high pressure of CO and high temperature), then a fairly strong d -
p* bond is established. .Electrons flow into the metal via the weak
-bonds and are back-donated into the p* orbitals through the d-
p* bond, a process referred to as synergic Interaction.
 Mechanism of Bonding in Metal Carbonyls
A weak -bond

p* -Orbital

M + CO M CO
d p* Orbital

d -Orbital
Note The Overlap of d p* Orbitals .This gives a strong Bond

Note: The bonding Mechanism in Isonitriles, the cyanides (ie.

Complexes containing CN- as a ligand,) and NO+, is very similar
to Bonding in metal Carbonyls. The Main difference between the
two types complexes is that whereas the M-C bond in metal
carbonyls is very weak, the metal-carbon bond in isonitriles and
cyanides are very strong. Also, the bond between metal and
Nitrogen in nitrosyl complexes is also strong.
The bonding mechanism in Carbonyl complexes has also been
used to explain bonding in dinitrogen complexes . These are
complexes which contain dinitrogen , N2, as a ligand. In this case ,
the metal-Nitrogen bond is found to be even weaker than a metal –
carbon bond as found in metal carbonyls.

Evidence for Back-donation In Metal Carbonyls:. The evidence

of back donation in metal carbonyls comes from a study of the
infrared spectra of such complexes. Thus, whereas the υ(C-O) in
gaseous carbon monoxide is observed at 2143cm-1, the frequency is
observed in the range 2000-1750cm-1 in co-ordinated terminal CO
groups and 1750-1650cm-1 in bridging CO groups .As is well-
known putting electrons into anti-bonding molecular orbitals
weakens a chemical bond. This is demonstrated very clearly by the
stretching frequencies for of similar carbonyl species which only on
the net negative charge at the central metal ion.
Species υ(C-O) ( cm-1) Δυ(C-O) ( cm-1)

CO 2143 …………………0
[Mn(CO)6]+ 2090 53
Mo(CO)6 2000 143
-
[V(CO)6] 1860 283
Among the three carbonyl species, the vanadium complex has
the highest net negative charge on the central metal ion and
hence, the largest amount of charge available for back donation .
This is the reason why,, among the three carbonyl complexes, the
largest decrease in stretching frequency is observed in this
complex.

Exercise. (
1 ) Explain why Cr(CO)6 is a stable species , Ca(CO)6 is not.
(2 ) List any three organometallic Complexes known to have
catalystic activity giving detailes of reactions catalyzed.
(3 ) A particular stretching mode in IR spectrum had an absorption
peak at 1700cm-1 . After a reaction , the same band was observed at
1650cm-1 . Suggest a possible reason for this observation .