Iorganic Chemistry III/ II

CHM-506/552
Crdt Hrs 4(3-1)
Metal carbonyl compounds
 Transition Metal Complexes
• transition metals have the ability to form complexes
with a variety of neutral molecules
• (carbon monoxide, isocyanide, substituted phosphine,
arsinies, stilbenes, nitric oxide) and
• various molecules with delocalized π-orbitals such as
(py) (2,2-bpy),(phen).
• Very diverse type of complexes exists, ranging from
binary molecular compounds Cr(CO)6 , Ni(PF3)4
• to complex ions such as [Fe(CN)5CO]3- , [Mo(CO)5I]1- ,
[Mn(CNR)6]+, [V(phen)3]+, [Mn(CO)5]-,
• In all these complexes metals are in low positive, zero
or even in negative formal oxidation state.
 π-acceptor ligands/Complexes
π-acceptor ligands have the ability to stabilize low
oxidation states of metals, e.g CO
π-acceptor ligands have vacant π –orbitals, in addition to
lone pairs, these vacant orbitals accept electron density
from filled metal orbitals to form a type of π- bonding ,that
supplements the σ-bonding arising from lone pair donation
M :π-acceptor ligand
Higher electron density on metal atom can thus be
delocalized onto the ligands.
 π-acidity.
The ability of ligands to accept electron density into
low-lying empty π-orbitals is called π-acidity.

Most important π acceptor ligand is CO

 Nobel gas formalism
 Stoichiometries of most complexes of π-acids ligands can be predicted by use
of nobel gas formalism
 “number of valence electrons possessed by the metal atom, plus the number
of electrons contributed by the ligands, be equal to number of electrons in
nearest nobel gas atom”
 18 e rule
 Basis for this rule is that metals tend to use their valence orbitals as fully as
possible.
nd, (n+1)s, (n+1)p
 This rule is of considerable importance for designing new compounds, i.e
metal carbonyls nitrosyls, isocyanides and their substitution products,
 Exceptions
V(CO)6 , [Mo(CO)2(diphos)2 ]+
diphos=1,2- bis(diphenylphosphino)ethane.
 This rule fails totally for bpy and dithiolene type ligands
 CO -Complexes
 CO-complexes are called carbonyles
 The first metal carbonyl compound described
was Ni(CO)4 (Ludwig Mond, ~1890), which was
used to refine nickel metal (Mond Process)
 Metal carbonyls are used in many industrial
processes
i.e., Monsanto process (acetic acid), Fischer
Tropsch process (vinyl esters)
 Vaska’s complex (IrCl(CO)(PPh 3)2) absorbs
oxygen reversibly and serves as model for the
oxygen absorption of myoglobin and hemoglobin
Classification of Carbonyles
Mononuclear carbonyles M(CO)x
CO CO CO
OC CO CO
M OC M M
CO
OC CO CO OC
CO
CO CO

M(CO)6 (Oh) M(CO)5 (D3h) M(CO)4 (Td)

i.e., Cr(CO)6 i.e., Fe(CO)5 i.e., Ni(CO)4
Dinuclear carbonyles M2(CO)x
CO O O
OC CO OC C C CO O O
CO OC C C CO OC CO CO
OC M M CO Fe Fe
OC OC CO Co Co OC Co Co CO
CO OC CO
OC OC OC CO
C CO OC CO
O OC OC

M2(CO)10 (D4d) Fe2(CO)9 (D3h) Co2(CO)8 Co2(CO)8

i.e., Re2(CO)10 (solid state, C2v) (solution, D3d)
 Mononuclear compounds M(CO)x

• Hydrophobic, Volatile and soluble in Non polar solvents

• d-block metal form stable Mononuclear Carbonyles obeying

nobel gas formalism

• Exception V(CO)6
• nobel gas formalism can be simplified to:

• 18 electron rule

• “Stable metal complexes will be formed when the some of

metal valence electrons & electrons donated by ligands equal
to 18”
 Table. Examples of neutral, binary metal carbonyls

4 5 6 7 8 9 10 11

Ti V(CO)6 Cr(CO)6 Mn2(CO)10 Fe(CO)5 Co2(CO)8 Ni(CO)4 Cu

Fe2(CO)9 Co4(CO)12
Fe3(CO)12

Zr Nb Mo(CO)6 Tc2(CO)10 Ru(CO)5 Rh4(CO)12 Pd Ag

Ru3(CO)12 Rh6(CO)16

Hf Ta W(CO)6 Re2(CO)10 Os(CO)5 Ir4(CO)12 Pt Au

Os3(CO)12
 18e- rule applied to mononuclear metal carbonyls .
Group VIA (6) metals (Cr,Mo,W)
• The stable binary carbonyls are M(CO)6
Reason
valence es- from each M = 6
Electrons from 6CO = 12
total electrons 18 es
• Stable derivatives of mononuclear carbonyls will be
those where one or more CO groups have been replaced
by an equal number of 2es- donors , so that total es-
provided by ligands remain 12.
W(CO)6+Cl- W(CO)5Cl+CO
Cr(CO)6+R2S Cr(CO)5SR2+CO
• Chloride anion and thioether are 2es- donors
 Mechanism of reaction
.
• Substitution reactions of group VIA (6) hexacarbonyls
proceeded by dissociative mechanism
Reason
the loss of a carbonyl ligand to give a 16 e intermediate is
more favourable than the gain of an extra ligand (associative
mechanism)
 Mechanism of reaction
.
 Group 8 (Fe, Ru, Os)
Fe(CO)5
• For iron it is the pentacarbonyl that is stable
( 8ve+10CO es=18es)

• Replacement of a CO ligand by 2es- donor is a common

reaction of Fe(CO)5
Fe(CO)5 + Py Fe(CO)4py+CO

Reaction proceed via dissociative mechanism

• Ru, Os also form pentacarbonyls but these monomers are

unstable and give polynuclear systems.
Fe(CO)5
• For iron it is the pentacarbonyl that is stable
( 8ve+10CO es=18es)

• Replacement of a CO ligand by 2es- donor is a common

reaction of Fe(CO)5
Fe(CO)5 + Py Fe(CO)4py+CO

Reaction proceed via dissociative mechanism

• Ru, Os also form pentacarbonyls but these monomers are

unstable and give polynuclear systems.
 Bonding modes of CO
Three bond modes found in metal carbonyl compounds

O O
O

C C C

M M M M M

terminal 2 3

The double bridged type occur frequently i.e Co2(CO)8,

Fe2(CO)9, as compared to or triply-bridged mode polynuclear
metals carbonyl i.e., Rh6(CO)16 (four triply bridged CO groups)
Which modes are present in a given compound can
be determined by infrared spectroscopy
 Bridging structures exists as tautomers

 Relative stability of structures a, and b depends on size of metal atom

 Larger the metal atom greater will be stability for non bridged structure
 Trend in a group

 Relative stability of non bridged structure increases down the group i.e
Fe3(CO)12 has two bridging carbonyls while Os3(CO)12, Ru3(CO)12 have none
 Trend in a period
Relative stability of non bridged and bridged structure

Mn2(CO)10 exists as non bridged structure

Co2(CO)8 exists as an equilibrium mixture of bridged
and non bridged structure
 Carbon Monoxide
 Carbon monoxide is a colorless, tasteless gas that is highly toxic
because it strongly binds to the iron in hemoglobin
 It is generally described with a triple bond because the
bond distance of d=113 pm is too short for a double bond
i.e., formaldehyde (d=121 pm)

 The structure on the left is the major contributor because both

atoms have an octet in this resonance structure, which means that
the carbon atom is bearing the negative charge
 The lone pair of the carbon atom is located in a sp-orbital
 Bond Mode of CO to Metals
 The CO ligand usually binds via the carbon atom to the metal

C O C O

-bond -backbond

 The lone pair on the carbon forms a s-bond with a suitable

d-orbital of the metal
 The metal can form a p-back bond via the p*-orbital of the
CO ligand
 Electron-rich metals i.e., late transition metals in low oxidation states are
more likely to donate electrons for the back bonding
 A strong p-back bond results in a shorter the M-C bond and
a longer the C-O bond due to the population of an anti-bonding orbital in
the CO ligand
 Synthesis
 Some compounds can be obtained by direct carbonylation at room
temperature or elevated temperatures
25 C/1 atm o
Ni(CO)4 -1
Ni + 4 CO (CO)= 2057 cm

150oC/100 atm
Fe + 5 CO Fe(CO)5 -1
(CO)= 2013, 2034 cm

CrCl3 + Al + 6 CO Cr(CO)6 + AlCl3 -1

(CO)= 2000 cm

Re2O7 + 17 CO Re2(CO)10 + 7 CO2 (CO)= 1983, 2013, 2044-1cm

CH3COOH
2 Fe(CO)5 Fe2(CO)9 + CO (CO)= 1829, 2019, 2082-1cm
UV-light

 In other cases, the metal has to be generated in-situ by reduction

of a metal halide or metal oxide
 Many polynuclear metal carbonyl compounds can be obtained
using photochemistry, which exploits the labile character of many
M-CO bonds (“bath tub chemistry”)
 Bonding Modes in MCO
 Three bond modes found in metal carbonyl compounds
O O
O

C C C

M M M M M

terminal 2 3

 The terminal mode is the most frequently one mode found

exhibiting a carbon oxygen triple bond i.e., Ni(CO)4
 The double or triply-bridged mode is found in many polynuclear
metals carbonyl compounds with an electron deficiency i.e.,
Rh6(CO)16 (four triply bridged CO groups)
 Which modes are present in a given compound can often
be determined by infrared spectroscopy
 Structures II
Mononuclear compounds
CO CO CO
OC CO CO
M OC M M
CO
OC CO CO OC
CO
CO CO

M(CO)6 (Oh) M(CO)5 (D3h) M(CO)4 (Td)

i.e., Cr(CO)6 i.e., Fe(CO)5 i.e., Ni(CO)4
Dinuclear compounds
CO O O
OC CO OC C C CO O O
CO OC C C CO OC CO CO
OC M M CO Fe Fe
OC OC CO Co Co OC Co Co CO
CO OC CO
OC OC OC CO
C CO OC CO
O OC OC

M2(CO)10 (D4d) Fe2(CO)9 (D3h) Co2(CO)8 Co2(CO)8

i.e., Re2(CO)10 (solid state, C2v) (solution, D3d)
 Infrared Spectroscopy
 Free CO: 2143 cm-1
 Terminal CO groups: 1850-2120 cm-1
 m2-brigding CO groups: 1750-1850 cm-1
 m3-bridging CO groups: 1620-1730 cm-1
Compound n(CO) (cm-1)
Ni(CO)4 2057
Fe(CO)5 2013, 2034
Cr(CO)6 2000
Re2(CO)10 1976, 2014, 2070
Fe2(CO)9 1829, 2019, 2082
Rh6(CO)16 1800, 2026, 2073
Ag(CO)+ 2185

 Non-classical metal carbonyl compounds can have n(CO) greater than the one observed
in free CO
 Application I
Fischer Tropsch Reaction/Process
 The reaction was discovered in 1923
 The reaction employs hydrogen, carbon monoxide and
a “metal carbonyl catalyst” to form alkanes, alcohols, etc.
 Ruhrchemie A.G. (1936)
Used this process to convert synthesis gas into gasoline using
a catalyst Co/ThO2/MgO/Silica gel at 170-200 oC at 1 atm
The yield of gasoline was only ~50% while about 25% diesel
oil and 25% waxes were formed
 An improved process (Sasol) using iron oxides as catalyst,
320-340 oC and 25 atm pressure affords 70% gasoline
 Application II
 Second generation catalyst are homogeneous i.e. [Rh 6(CO)34]2-
 Union Carbide: ethylene glycol (antifreeze) is obtain at high
pressures (3000 atm, 250 oC)
O
CO H2 H2 CO
M M CO M C H M CH3 M COCH3
H2 H2 H2

O H
M M CH2 CH3
CH2 M CH3
H2 CO
M
CH3OH M OCH3
CH4 M COCH2CH3

M H

Gasolines

 Production of long-chain alkanes is favored at a temperature

around 220 oC and pressures of 1-30 atm
 Application III
 Monsanto Process (Acetic Acid)
 This process uses cis-[(CO)2RhI2]- as catalyst to convert methanol
and carbon dioxide to acetic acid
 The reaction is carried out at 180 oC and 30 atm pressure
CH3
Oxidative I CO CO Insertion
Rh
Addition CO
I
I
CH3OH CH3I
COCH3
I
I CO
HI H2O Rh
Rh
I CO
I CO
I

CH3COOH CH3COI

COCH3
I CO
Rh
Reductive I CO CO
Elimination I CO Addition

 Two separate cycles that are combined with each other

 Application IV
Hydroformylation
 It uses cobalt catalyst to convert an alkene, carbon monoxide and
hydrogen has into an aldehyde
 The reaction is carried at moderate temperatures (90-150 oC) and
high pressures (100-400 atm)
HCo(CO)4

CO
RCH2CH2CHO HCo(CO)3
CH2=CHR

RCH2CH2COCo(H2)(CO)3 HCo(CO)3(CH2=CHR)

H2
RCH2CH2COCo(CO)3 RCH2CH2Co(CO)3

RCH2CH2Co(CO)4 CO
 Application V
Reppe-Carbonylation
 Acetylene, carbon monoxide and alcohols are reacted in the
presence of a catalyst like Ni(CO)4, HCo(CO)4 or Fe(CO)5
to yield acrylic acid esters
 The synthesis of ibuprofen uses a palladium catalyst on the
last step to convert the secondary alcohol into a carboxylic
acid

(CH3CO) 2O/HF H2, Raney Ni CO, [Pd]

O OH COOH
 Application VI
Vaska’s Complex (1961)
 Originally synthesized from IrCl3, triphenylphosphine
and various alcohols i.e., 2-methoxyethanol.
 Triphenylphosphine as a ligand and reductant in the reaction
 A more convenient synthesis uses N,N-dimethylformamide as
the CO source
 Aniline is frequently used as an accelerant
 The resulting bright yellow complex is
square planar (IrCl(CO)(PPh3)2) because
Ir(I) exhibits d8-configuration CO
 The two triphenylphosphine ligands are Ph3P Ir PPh3
Cl
in trans configuration.
 Application VII
 Vaska’s Complex (cont.)
 The carbonyl stretching mode in the complex is consistent with a strong
p-backbonding ability (d(CO)= 116.1 pm (free CO, d= 113 pm))
 The complex is a 16 VE system that reactants with broad variety of compounds
under oxidative addition usually via a cis addition in which
the Cl and the CO ligand fold back
CO X Y
X- Y
Ph3P Ir PPh3 Ph3P Ir PPh3
Cl Cl CO

 Note that a molecule like oxygen is bonded

side-on in the light orange complex:
 d(O-O)=147 pm (free oxygen: 121 pm, peroxide (O 22-:149 pm))
 n(O-O)=856 cm-1 (free oxygen: 1556 cm-1, peroxide (O22-: 880 cm-1))
 Note that the older literature reports a d(O-O)=130 pm, which is more
consistent with a superoxide (O2-)!
 The addition of oxygen to Vaska’s complex is reversible
 Application VIII
 Vaska’s Complex (cont.)
X-Y n(CO) in cm-1
none 1967
H2 1983
O2 2015
HCl 2046
MeI 2047
I2 2067
Cl2 2075

 The resulting products exhibit increased carbonyl stretching

frequencies because the metal does less p-backbonding due to its
higher oxidation state (Ir(III))
 A similar trend is also found for the Ir-P bond length, which increases
in length compared to the initial complex