37

(REDUCTIVE CARBONYLATION)

(CO itself acts as a reducing agent and get converted to CO2 in the process.
The reaction conditions are relatively more drastic for such reactions)

38
 Reactions of Metal Carbonyls

1. Reduction : Carbonyl anions

V(CO)6 + Na Na[V(CO)6]

Mn2(CO)10 + 2Na 2 Na[Mn(CO)5]

Co2(CO)8 + 2Na 2 Na[Co(CO)4]

Fe(CO)5 + Na/Hg Na 2Fe(CO)4

2. Oxidation : Iodocarbonyls
Mn2(CO)10 + I2 2 Mn(CO)5I

Fe(CO)5 + I2 Fe(CO)4I2

3. Photochemical substitution
h W(CO)5(PPh3) + CO
W(CO)6 + PPh3
In the presence
Fe(CO)5 + h of UV radiation
Fe(CO)3 + 2CO
a monodentate
ligand displaces
only one CO unit

39
40
 PROPERTIES OF CARBONYL HYDRIDES

The term hydride is assigned based on the formal oxidation state, however, the
properties of organometallic hydrides vary from hydridic to protic in character.

The carbonyl hydrides of transition metals behave as both acid as well

as base. The strong π-acceptor ligands such as CO have strong
electron withdrawing character and leads to the polarization of the M-H
bond in HM(CO)n complexes.

Based on the nature of metal and ligands, the acidity of these complexes varies significantly.

• The acidic character of metal carbonyl hydrides decreases on descending the group in
periodic table.
• Bridging hydrides are more acidic than complexes with terminal M-H.
• The σ-donor ligands such as Cp, phosphines, etc. reduce the acidity of M-H bond,
whereas, π-acceptor ligands such as CO, NO, PF3 increases the acidity of M-H bond.

HCo(CO)3(PMe3) < HCo(CO)3(PPh3) < HCo(CO)3(PF3)

41
 Reactions of Metal Carbonyls

6. Nucleophilic addition to CO
R OLi R OCH3
CO
C C
OC CO OC
OC CO [Me3O]BF4 CO
W RLi W
W
OC CO OC
ether OC CO CO
OC OC
OC
Fischer Carbene
Carbenes are catalysts
for olefin metathesis
Et
Et
Al
7. Migratory insertion of CO O
Et
O CO CO
C 2 AlEt3 C
Me
Me
Fe Fe Fe OFe
CC
C OC
OCOC OCO O
CO
OC CO
Mn Et AlMn
OC CO high pressure Et Et
OC CO
OC
OC

42
Photochemical Substitution
Photochemical substitutions are the most common photoreactions in organometallic chemistry.
Kinetic studies have shown that the rate constant for the dissociation of one CO unit which
precceds the entrance of a new ligand is increased upon photochemical excitation by a factor of
1016. h
W(CO)6 + PPh3 W(CO)5(PPh3) + CO

Fe(CO)5 + h
Fe(CO)3 + 2CO

Photochemical excitation of a metal carbonyl with a mixed substituent coordination sphere causes dissociation
of a ligand which is most weakly bonded in the ground state as well. If ligands of comparable ligand strength
are used one can displace all the carbonyl groups

If after dissociation of a ligand no suitable free ligands are present the free coordination site generated
through photochemical dissociation of CO may get closed by dimerization. The gap may also be filled internally
by an 1 to 3 rearrangement
Br
2 Re(CO)5Br
h
(CO)4Re Re(CO)4
Br
Mn(CO)5 h
- CO Mn(CO)4
43 43
 Alkene and Alkynes As Ligands
Zeise’s Salt - The first transition metal organometallic compound

Discovery 1827
Structure ~ 150 years
W C Zeise, Danish later
pharmacist, I789- I847 Potassium trichloro(ethylene)platinate(II)

• Ethylene molecule occupies the 4th coordination site of square planar complex with
its C-C axis perpendicular to the platinum-ligand plane.

• Alkene can bind to metal center and act as both σ donor and π acceptor.

• Relative to the free ethylene, the C-C bond in the complex is lengthened slightly and
the hydrogens are slightly tilted back from the planar arrangement.

44
 Models of Ethylene-Metal Bonding
• Two Models: Dewar-Chatt-Duncanson Model
and Metallacyclopropane Model.
• Structural studies on a large number of alkene
complexes have shown that they fall in between M M
these two extremes depending on the M and
Dewar-Chatt cyclopropane
substituents on the alkene carbon atoms.

For Zeise’s salt, the best bonding picture is given by the Dewar-Chatt-Duncanson
model. This involves the donation of the C=C  electrons to an empty d sigma
orbital of the metal, accompanied by back donation from a filled metal d orbital
into an empty C=C * orbital.

C C
M  M *
C C

donation from  back donation to *

Dewar- Chatt - Duncanson Model
As the back donation for the metal is important to stabilize the complex only soft
metals capable of back donation binds alkenes. 45
Bond distances of few platinum-alkene complexes
Pt(+2) Pt(0) Pt(+2)

(Zeise’s Salt)

Dewar-Chatt-Duncanson In between Metallacyclopropane

Model two models Model

46
 Metallacyclopropane Model
In the metallacyclopropane extreme, the substituents on the
carbon are strongly folded back away from the metal and the
carbons rehybridize from sp2 to somewhat more closely to a sp3.
In this process, the metal gets oxidized and its formal oxidation
state increases by two units, the C-C bond lengths become more
of a single bond.

• The 2- Pt and Pd complexes of C60 come under this category.

47
• When the back bonding from the metal atom to the alkene ligand is
small, substituents on the alkene are bent only slightly away from the
metal and the C-C bond length is lengthened marginally from the free
alkene (Dewar-Chatt-Duncanson Model).

• With electron withdrawing substituents on the alkene, the back

donation is greater and substituents on the alkene are bent more
backwards and the C-C bond length approaches that of a single bond
(Metallacyclopropane Model).

M M
Dewar-Chatt cyclopropane

48
 Examples of complexes with alkenes having electron withdrawing groups

The electron withdrawing fluoro groups in F2C=CF2 as well as cyano groups of

(NC)2C=C(CN)2 make them better π-acceptor ligand. This effect weakens the C=C bond
but strengthens the alkene-metal bond.

49
Important Points

50
Effect on alkene stretching frequency ( νC=c)
Both σ donation and π back bonding weaken the C=C bond resulting in
the lower νC=c stretching frequencies compared to the free alkene in the
infrared spectra.

CH2=CH2 νC=c = 1623 cm-1

Fe(CO)4(CH2=CH2) νC=c = 1551 cm-1
Pd2Cl4(CH2=CH2) νC=c = 1525 cm-1
Pt2Cl4(CH2=CH2) νC=c = 1506 cm-1
CpRh(CH2=CH2)2 νC=c = 1493 cm-1

51
 Alkynes: Modes of Bonding to Metals
• Alkynes are essentially like alkenes, only with another perpendicular pair of -
electrons. Thus they can act as neutral 2 or 4 e- donors, depending on the needs
of the metal center. They are also much better bridging ligands because of this
second set of -electrons.
• Alkynes are better donors compared to alkenes and typically coordinate far more
readily to a metal for steric (more open, less hindered) and electronic (better donor,
2 or 4e- bonding) reasons.

C C C C

M M

R R R
R R R
C C C C
C C

M M M M M M
Possible modes of binding of alkynes to metal centers
52
Synthesis of metal – alkyne complexes
R
R
C
C
Co2(CO)8 + R-C C-R
(CO)3 Co Co (CO)3

But
Cl

But2C2, EtOH H2NR Pt

Na2[PtCl4]
4-MeC6H4-NH2
Cl
But

But

PPh3
Ph2C2, Pt
(Ph3P)2Pt(C2H4)
PPh3

But 53
Reactions of Metal Complexes of Alkenes and Alkynes
• With cobalt and palladium compounds alkynes dimerize to give cyclobutadienyl
compounds

Oxidative
coupling

Co(+1) Co(+3)

54
• The most interesting reactions of alkynes with transition metals is the
trimerization of alkynes by cobalt, nickel and palladium salts.
• Example: acetylene and substituted acetylenes trimerise to benzene or its
derivative in the presence of catalysts like CpCo(COD) or CpCo(C2H4)

• Trimerisation reactions also occur with a combination of alkyne and nitriles or

analogous compounds to yield pyridine derivatives.

55 55
 Problems
Q1. Reaction of two moles of CpNa with MCl2 gave an unstable compound A with molecular
formula C10H10M (M is a first row TM). On reacting A with excess of a hydrocarbon gas B along
with K gave a stable compound C with the empirical formula C9H13M. Reaction of C with excess
diphenylacetylene gave a highly stable compound D with the molecular formula C29H25M along
with evolution of the gas B. Write the structures of compounds A to D.
Ans:

Q2. Which of the following metal alkene complexes do you think will look more like a
metallacyclopropane? Explain your answer.
(a) (CH2=CH2)Ni(PPh3)2 (b) (CH2=CH2)Fe(CO)4
Ans: (a) (CH2=CH2)Ni(PPh3)2, since it has a more electron rich metal.
Q3. Arrange the following compounds in the increasing order of ethylene C-C bond lengths

Ans: B<A<C<D
56
Q4. Predict the product(s) in the following reactions.

Q5. To which of the following structures will trifluoroethylene (F2C=CHF) bind most and least strongly?

Ans: bind strongly least strongly (d0)

57