LECTURE 6: METAL CARBONYL

PROF LYDIA W. NJENGA

Dept Chemistry
UON
 Introduction expected outcome of the course

 The carbonyl ligand, CO, is the most common ligand in organometallic chemistry
 The compounds formed by CO and transition metals are referred to metal
carbonyls
 The CO contributes electron to the metal (OC→M), hence metal is mostly in low
oxidation state (zero oxidation state).
 It serve as the only ligand in binary carbonyls (homoleptic complexes), Examples:
Ni(CO)4, W(CO)6, and Fe2(CO)9, or,
 in combination with other ligands (heteroleptic complexes) e.g
OsCl2(CO) 2(PPh3) 2, [(η5 –C5H5)Mo(CO)3]2. CO

 It will bond to a single metal, or it may serve as a bridge between two or more
metals
Cont’d
Depending on the number of metal atoms, in a given carbonyls, they may be
classified into two groups:
1. Mononuclear (or monomeric) Carbonyl
 Carbonyls which contains only one metallic atom per molecule and are of
the type M(CO)n.
 Examples V(CO)6, Cr(CO)6 Ni(CO)4
Cont’d

2. Polynuclear carbonyls:
 They contain two or more metallic atoms per molecule and are of the type
Mx(Co)y. They may also be referred as bridged (Have terminal CO and Bridged
CO)
 May be homonuclear; Fe3(CO)12 , Mn2(CO)10 , Co2(CO)8
 Or Heteronuclear; MnCo(CO)9, MnRe(CO)10
Bonding
Review on bonding
Refer to SCH 304: The following was covered

Valence Bond Theory

Crystal Field Theory

Molecular Orbital Theory

Metal carbonyl (M-CO)
 To understand bonding in M-CO it is important for us to look at the bonding of
CO
 Carbon monoxide: important -acceptor ligand and good ϭ donor
 Reacts with the transition metals in low oxidation States (-1, 0, +1) to form stable
complexes with respect with oxidation, dissociation and substitution
 Both C and O are diagonally sp hybridised (s and pz) with one hybrid in each atom
with a lone pair of electron
 Sigma bond formed hybridised sp ( s and pz orbitals) – linear (one hybrid on each
atom with a lone pair of electrons.
 Overlap to form Sigma bonding (б) both bonding and antibonding
 Unhybridized py and px overlap to form two  (bonding) orbitals and two *
(antibonding) orbitals
 oxygen is more electronegative than carbon, hence, will be at a lower energy level
 Coordination hybrid orbitals Shape
number
2 sp Linear

3 sp2 Trigonal planar

4 sp3 Tetrahedral (Td)

4 dsp2 square planar

5 dsp3 Trigonal bipyramid

5 sp3d Square pyramid

6 d2sp3 or sp3d2 Octahedral (Oh)

Fig 1 MO Energy diagram of CO showing the π orbitals

Pi*

PC
PO

Pib
The four electrons in the p orbitals will occupy the  bonding orbitals and * will be
empty.
 Bonding in Metal Carbonyl
 Metal contain partially filled d orbitals (or presence of empty d orbitals)
 Two bonds are formed:
1. First dative overlap between empty d orbitals and the filled carbon б (sp) orbital.
➢ The lone pair of electron from carbon occupies the empty d orbitals making the
metal to have excess of electrons

2. Second dative overlap of filled d or hybrid dp metal orbital with the empty *
of the CO.
➢ The electrons from the metal d orbitals are donated back to the empty * orbitals
of the carbonyl.
➢ The CO * orbitals help to drain excess negative charge from the metal onto the
ligands (Ligands with empty  orbitals are called  acid ligands)
Diagram showing the synergic bond (Back bonding) formation

This kind of bonding mechanism is called synergic bond (The mutual reinforcement
whereby there is a back bonding). i.e The ϭ-donor and π-acceptor interaction in CO
complexes syneegistically reinforce each other. This synesgistic effect is called the
Dewar-Cahtt-Duncanson model for carbonyls
Example of Cr(CO)6 (3d3)

Cr has a total of 9 Valence orbitals-

The 3d (5) orbitals are split into:

❖ eg orbitals (dz2, dx2-y2) of higher energy and

❖ t2g orbitals (dxy, dxz, dyz) of lower energy which are the ones occupied by
3 electrons.

 The vacant 3d (eg), 4s (1) and 4p (3) orbitals hybridize to form six Oh d2sp3
hybrids orbitals (ϭ) which act as acceptors for lone pairs donated from the
6CO groups
❖ These six forms the sigma (ϭ) bonds which take the 12 electrons from
6 ligands
Cr orbitals in Oh field

Atomic orbitals Molecular deneracy

orbitals
S (1) a1g singlet
P (3) t1u Triply degenerate

dx2-y2, dz2 (2) eg Doubly degenerate

dxy, dxz, dyz (3) t2g Triply degenerate

MO showing formation of ϭ bonding

Note
T1u*
 the orbitals of the ligands and
metal which have overlapped T1u
A1g* Eg* weakly antibonding

to form ϭb and ϭ* bonding

 the ligand orbitals are lower A1g Eg*

in energy.
∆o
 E of the ligand occupy the ϭb Eg + T2g non bonding
T2g
A1g + Eg +TU

orbitals 3d

Metal ions Eg
Orbitals A1g
 the t2g orbitals of the metal T1u Ligand
are non-bonding Molecular Orbitals Orbitals
Cont’d

Always, the б orbitals [a1g (1), eg, (2) t1u(3)] of the metal will overlap
with б orbitals ((a1g, eg, t1u) of the ligands while the  orbitals
(t2g) of the metal overlap with  orbitals (t2g) of the ligands if
present . Otherwise, they will remain nonbonding like above case.

 Only orbitals of the same symmetry will overlap

Overlap of  orbitals

Note
 The ligand  orbitals are higher in
energy than the metal  orbitals.

 The electron from t2g () orbitals of

the metal will occupy the b
orbitals
Mo Energy diagram of Cr(CO)6 (both б and π orbitals
Cont’d

 Some of the physical evidence used to show the existence of multiple nature of
the M-CO bonds are:

❖ bond lengths and

❖ vibration spectra

 When the electrons from the metal drift into CO orbitals:

❖ the CO becomes negative and hence increases its basicity through the  orbital of
carbon,
❖
❖ at the same time a drift of electrons to the metal in  bond tend to make CO positive
hence enhancing the acceptor strength of the б orbitals from carbon
 What do you think will happen to the bond when this reinforcement takes place?

 M-C becomes stronger (M-C bond becomes shorter)

 while the C≡O becomes weaker (C≡O bond becomes longer)
➢ C≡O 1.128 Ao (CO itself)
➢ M-C ≡O 1.15 Ao
 To study M-CO multiple bonds-
 Vibration modes rather than bond length are used
 CO stretching frequencies (gives stronger bands) than M-C
 M-C stretching frequency are not used.
 Other - acceptor ligands
Other ligands related to CO
1. NO Contributes 3e (forms nitrosyl cpd-diamagnetic)
 NO+ Contributes 2 e complexes formed by NO conform to EAN rule
 Hence it is possible to obtain isostructural series such as Ni(CO)4, Co(CO)3NO,
Fe(CO)2(NO)2 and Mn(CO)(NO)3.
 Question: Calculate the EAN of the above molecules
 Remember NO is a 3e-donor in covalent model: 2NO = 3CO in electron-count while
NO+ will donate 2e- in ionic model). Hence direct displacement of CO with NO gives
products of a different stoichiometric.
Replacing CO with NO+ means the complex will have an extra positive (or one less
negative) charge
➢ NNR+, N2, CN- and CNR are isoelectronic CO and NO
➢ Coordinate via p orbitals to form d- p.
 Cont’d

2. -acceptor ligands are from group (15) R3P, R3As or R3Sb (R-alkyl, aryl or
halogen), and group (16): R2S, R2Se or R2Te (R=alkyl or aryl).

 the L→M  bonding takes place through the lone pairs of electrons on the P, As,
Sb etc. atoms

 but L←M back donation takes place into vacant d orbitals of these atoms. Such
orbitals have the correct symmetries and suitable energies. This is known as d-
d –bonding
Cont’d

3. The third type of  acceptors ligands are those of the heterocyclic

molecules such as pyridine and 2,2-bipyridyl and the define groups which
posses' double bonds (Benzene, C5H5 etc).

 The N atom lone pairs of pyridine are the  donors' orbitals but the
acceptor orbitals are the vacant antibonding (*) aromatic orbitals which
extend over the whole aromatic ring system.

 Ligands such as R, F-, Cl-, are  donors (P) after one lone pair is used to
form M-L б bonds
PREPARATION OF METAL CARBONYL

 Metal carbonyls are very important in everyday life and hence it is necessary for you to
know how you can prepare them.
 four methods are used:

a) Direct reaction of a metal with CO (finely divided metal + CO).

b) Reductive Carbonylation in which metal salt is allowed to react
with CO in the presence of a reducing agent (which also may be
carbonyl).
❖ This will reduce the metal from the positive state to the lower states of 1, 0, -1, -2

c) Thermal or photochemical reaction of other binary carbonyls

d) Displacement Reactions
a) Direct reaction

 Only Fe and Ni react directly with CO under non vigorous condition to

give Fe(CO)5 and Ni(CO)4 both of which are toxic.

Fe + 6CO (2000c/100atm) → Fe(CO)6

Ni + 4CO (RT, 1ATM) → Ni(CO)4 (Bases of Mond process)

2Co + 8CO (2000c/100atm) → (Co2(CO)8


b) Reduction
a) Reduction of acetates with H2 in presence of CO and sufficient acetic
anhydride.
Co(H2O)4(CH3CO2)2 + 8(CH3CO)2O +8CO + 2H2 →Co2(CO)8 + 2CH3CO2H.

(b) With anhydrous salt, Al/Mg is used as a reducing agent.

CrCl3 + A1 + 6CO (AlCl3/C6H6) → Cr(CO)6 + AlCl3

2MnI2 + 10CO + 2Mg → Mn2(CO)10 + 2MgI2

2Cr(acac)3(pyridine) + 12CO +Mg (1600c,300atm) → 3Mg(acac)2 +Cr(CO)6

Cont’d

c) CO may also function as a reducing agent.

Re2O7 + 17 CO → Re2(CO)10 + 7 CO2.
Os4 + 5CO (2500c,350atm) → Os(CO)5 + 2O2

d) Higher Carbonyls can be prepared by thermolysis of the lower ones:

3Os(CO)5→Os3(CO)12 + 3CO

 Such reactions occur because M-CO bond cleavage produces unsaturated

fragments that combine into nuclearity species
c) Thermal or photochemical reaction of other binary
carbonyls
 Photochemical cleavage is also employed as in the synthesis of di-iron
enneacarbonyl.

2 Fe(CO)5 + sunlight (or UV light) → Fe2(CO)9 + CO (dark yellow solid).

Os(CO)5 + sunlight (or UV light) → Os2(CO)9 + CO

Co2(CO)8 (50oc) → Co4(CO)12 (black solid)

Co2(CO)8 (60oc/EtOH) → Co6(CO)16 (black

Displacement Reactions

Below reaction takes place since CO is a reducing agents and can

react with other metal compounds.

2IrCl3 + 11CO → Ir2(CO)8 + 3COCl2

General properties
 State: Most of metal carbonyls are liquids or volatile solids eg, Ni(CO)4

 Colour: Most of the mononuclear carbonyls are colourless to pale yellow. V(CO)6 is a
bluish-black solid. Polynuclear carbonyls are dark in colour.

 Solubility: They are soluble in organic solvents eg glacial acetic acid, acetone,
benzene, carbon tetrachloride and ether.

 Toxicity: They have low Mpt and poor thermal stability, hence, show toxicity related to
the corresponding metal and carbon monoxide eg
❖ Exposure to these compounds can cause damage to the lungs, liver, brain and kidneys.
❖ Nickel tetracarbonyl exhibits the strongest inhalation toxicity.
❖ These compounds are carcinogenic over long-term exposure.

 Oxidation state: metals in low OS -1, 0, +1

 Properties Cont’d
 Magnetic Property:
❖ The metals with even atomic number form mononuclear carbonyls.
❖ Metals with odd atomic number form dinuclear metal carbonyls. Thus, all the electrons in the metal
atoms are paired. diamagnetic
❖ The unpaired electrons are utilized for the formation of metal-metal bonds.
❖ Hence these are generally diamagnetic in nature except V(CO)6 which is paramagnetic. (presence of one
unpaired electron)
 Thermal Stability:
❖ Most of the metal carbonyls melt or decompose at low temperatures. Solid carbonyls sublime in a
vacuum, but they undergo some degree of degradation.
 Thermodynamic Stability:
❖ thermodynamically unstable. undergo aerial oxidation at different rates.
❖ Co2(CO)8 and Fe2 (CO)9 are oxidized by air at room temperature, while
❖ chromium and molybdenum hexacarbonyl are oxidized in the air when heated
Study questions

1. What are the two primary binding modalities that CO ligand exhibits?

2. Why do low valent metal centers in metal carbonyl complexes stabilize

CO binding?

3. Even though O is more electronegative than C, CO has a dipole moment

of virtually zero. Explain.
Reactions of metal carbonyl
1. Dissociation of CO
➢ Initiated thermally or UV light

➢ Reduction with metal

Co2(CO)8 + 2Na → 2 Na[Co(CO)4]
➢ Loss of CO from 18e system to give 16e system (depend on complex and
its environment)

➢ The common reaction is where CO gp is replaced by another ligand to

form an 18e cpd
➢ Cr(CO)6 + PPh3 (Δor hv) → Cr(CO)5(PPh3) + CO
Dissociation of metal carbonyl cont’d

• It is a two-step pathway which corresponds to the SN1 reaction

• The system changes from 18e to 16 e and finally to 18 e system
Substitution reaction
 SN1: Dissociative and
 SN2 :Associative mechanisms
 ligands which have varying degrees of pi-acceptor ability

i) Neutral ligands: PX3, PR3, AsX3, AsR3, OR2, RNC

 For the Phosphines and arsines, empty 3d and 4d orbitals are ased rspectively and therefore
acts as  acceptors.

ii) Organic ligands: C6H6, C5H6, C7H8

 In alkenes empty * orbitals are used while in aromatic systems the * molecular orbitals of
the ring are used
iii) Bases: H-, OH-, NH2

iv) Halides: F-, Cl-, Br-, I-

Cont’d

 Examples
 Ni(CO)4 + 4CNR(Isocyanide) → Ni(CNR)4 + 4CO

 Ni(CO)4 + 2PPh3 → Ni(PPh3)2(CO)2

 Ni(CO)4 + 4PCl3 or 4PF3 → Ni(PCl3)4 or Ni(PF3)4 + 4 CO

 PPh3 can only displace 2 CO groups in Ni(CO)4 Why?

Question: Explain why PX3 is a better π acceptor than CO

Answer: PX3 is a better  acceptor than CO since the 3d orbitals of Phosphorous accept
the -electrons.
Cont’d

 Fe(CO) 5 +2 C5H5 → [Fe(CO) 2 (C5H5] 2

reflux SnCl2 or GeCl2
PbCl2
 [Fe(CO)2(C5H5] 2 SnCl2

 Mn2(CO)10 + Na/Hg → NaMn(CO)5

 ↓ Re(CO) 5 Cl

 (CO)5Mn-Re(CO)5
2. Formation of Metal carbonyl anions

 In presence of donor solvent

 3Na + Cr(CO)6 (NH3 solvent) → Na2[Cr(CO)5] + CO

 3Na + Fe2(CO)9 (NH3 solvent) → 2Na2[Fe(CO)4]2- + CO

Reaction with halogens and NO

 [Fe(CO)5 + X2 → [Fe(CO)4X + CO

 [Mn(CO)6 Cl2 → [Mn(CO)4Cl2 + 4CO

 They react with the NO (Nitric oxide) to form metal carbonyl nitrosyls

 Fe(CO)5 + 2NO → [Fe(CO) 2(NO)2 + 3CO (how many

electron is NO contributing)
Stability trends of the CO. Attribution: W. Petz
Stability Cont’d

 Overall, the stability of carbonyls tends to decrease from group 6 (Cr) to group 8 (Fe)
to group 10 (Ni)

 For the best orbital overlap for π-acceptor interactions, octahedral shape > trigonal
bipyramidal tetrahedral shape.

 There is a decline in stability from the 4th to the 6th period

❖ due to less efficient orbital overlap caused by the increasingly different orbital size
between the ligand and the metal orbitals.

❖ These effects are sufficiently large for Pd(CO)4 and Pt(CO) 4 to make them unstable.
Factors affecting substitution
The degree of substitution is limited by a combination of various factors. For
example
a) Ligand size
➢ PhO)3P and (MeO)3 P. (PhO)3P ligand will not replace more than 3 CO groups in
Mo(CO)6 while (MeO)3 P will replace all 6CO. This is due to its big size which
produces steric effect in comparison to the small size of (MeO)3 P.

b) -acceptor ability of the incoming ligand

 weaker - acceptor than CO and most are, then the amount of M to L bonding
may limit the L→M  bonding and a weak bond results

 If L does not accept d electrons, then the maximum M-C bond order will be
reached in a L3M(CO)3 (only 3CO are substituted and the remaining 3 will
share the 6 e left)
What are the consequences of substitution?

 Replacement brings change in frequencies and also the number IR active C-O
stretching vibration modes
❖ When C-O bond in free CO is stretched there is a dipole change and the absorption
will occur at a frequency of 2150 cm-1.

 2. If the CO molecule is coordinated, through the M-C  - bonding into the CO *

orbitals, a weakening of the C-O bond occurs → easier to stretch the bond
❖ Reduction in energy between ground and excited state
❖ decrease in frequency of the CO stretching bond
 In L-M(CO)5 replacement of CO by weaker  -acceptor means that the remaining 5
CO must accept more electrons from the metal and so the C-O bond orders decreases.
 The order of the  -acceptor ability of some ligands.
 L = CO > P(OR)3 > PPh3 > pyridine > amines
Resonance of M-CO bond

 Resonance structures of a metal carbonyl, from left to right the

contributions of the right-hand-side canonical forms increase as
the back bonding power of M to CO increases.
Study questions

1. Explain why (PhO)3P will only displace 3CO groups in M(CO)6 while (MeO)3P will displace
all the 6CO groups
2. Define the term isoelectronic ions
3. What do you understand by the term synergic bond?
4. Which of the following should be most stable? Explain your answer.
Fe(CO)2(NO)3; Fe(CO)6; Fe(CO)3; Fe(CO)2(NO)2; Fe(NO)5
5. Draw the structure of the product in each of the processes indicated.
i) Mo(CO)6 reacting with excess pyridine
ii) The reaction of cobalt with CO at high temperature and pressure
iii) Mn2(CO)10 reacting with NO

iv) Fe(CO)5 reacting with cycloheptatriene

6. How is benzene bound to Cr in the compound Cr(CO)3 (C6H6)? Explain your answer
Cont’d
7. Infrared spectra of Ni(CO)4 , CO(g), Fe(CO)42- , and Co(CO)4- have bands at 1790, 1890,
2143, and 2060 cm-1, respectively. Match the bands to the appropriate species and explain
your line of reasoning
8. Consider the positions of the CO stretching bands in the following complex and provide an
explanation. trans-[Ir(CO)Cl(O2 )] 2015 cm1-
9. Starting with ferrocene, predict how you could prepare the following.
a) (C5H5 )Fe(C5H4 CH3);
b) (C5H )Fe(C5H4 NO2)
10. Complete the following reactions
Fe(CO)5 + 2NO →
Co2(CO)8+ 2NO →
Fe3(CO)12 + 6NO →
11. Calculate the EAN of; i) [Co-(CO)2(NO+) 2], ii) [Fe2-(CO) 2(NO+)2]
iii) [Mn2-(CO) 2(NO+)2]
Characterization of Metal Carbonyls

 IR spectra
 Vibration frequency for carbon monoxide (CO) is 2143 cm-1. :
 The terminal carbonyl group (CO) stretching frequency appears at 2125 – 1850 cm-1.
 For the bridging CO denoted μ2-CO (μ-CO) the bond stretching frequency νCO is usually
shifted by 100–200 cm−1 to lower energy compared to the signatures of terminal CO,
which are in the region 1800 cm−1
Isoelectronic Carbonyls
a) When negative charges are present, the metal has excess electrons hence the electrons
must be taken from the metal by the carbonyl group, and this lowers the frequency from
2000 cm-1 to 1858 cm-1.

(b) A higher increase in negative charge will lowers the frequency even more.
 For example, in Fe(CO)42- due to presence of -2, the frequency has been lowered to
1788 cm-1
Cont’d

 Conversely, if we bring a change which would tend to inhibit the shift of

electrons from metal to CO, for example, placing a positive charge on the
metal, (Mϭ+- CO) the CO frequencies will increase.

 The metal is deficient of electrons due to loss of electrons therefore,

 the carbonyl electrons will flow towards the metal to minimize the increase
positive charge in the M

 Examples: In Mn(CO)6+ , the CO stretch frequency appears at 2095 cm-1

instead of 2000 cm
Substitution
 Changes in C-O stretching vibrations occur when other ligands are present. For example,
the CO stretching band in Cr(CO)6 is found at 2000 cm1 , whereas that in Cr(NH3) 3(CO)3
is found at approximately 1900 cm-1

 In this case, the product is the isomer in which all NH3 ligands are trans to the CO
molecules.
 Ammonia does not form π bonds to metals because it has no orbitals of suitable energy or
symmetry to accept electron density.

 Therefore, back donation from Cr in Cr(NH3)3(CO)3 goes to remaining 3CO

molecules, and the bond order is reduced even more than it is in Cr(CO)6 , in which back
donation occurs equally to six CO molecules.

 An increase in Cr-C bond order occurs and stretching frequency in Cr(NH3)3(CO) 3

compared to Cr(CO) is lowered
a) An increase of negative charges

Fe(CO)42- Co(CO)4- Ni(CO)4

 Note an increase of the negative
charges lowers the frequency.
1788 2002 2131  Increase of negative charges is
relieved by back donation of e to
the CO groups
1786 1890 2058
b) Increase of positive charge (The cpds are Isoelectronic)

 In a positively charged species, e.g

V(CO)6- Cr(CO)6 Mn(CO)6+ Mn(CO)6+, the resultant charge on the
metal atom may be kept close to zero by
2020 2119 2192 less M-C -bonding as compared to
neutral Cr(CO)6.
 metal has a progressively greater
negative charge that is partially relieved
1894 2027 2125
by back donation.
 There is, in fact, more reduction in C-O
bond order because the metal has a
1858 2000 2095 higher negative formal charge.
Substitution of the carbonyl gp by other ligands νCO cm-1

Cr(en)(CO)4 2016 2006 1880, 1816

Cr(dien)(CO)3 1900, 1760

Mn2(CO)10 2052 2019 1987

Mn(CO)5Cl 2138 2054 1999

Mn(CO)5Br 2133 2050 2001

Mn(CO)5I 2125 2044 2003

 (If other ligands are present that
cannot accept electron density,
more back donation to CO occurs Ni(CO)4 2131 2058
so that the M-C bond will be
stronger while C-O bond will
weaken)
(CH3)3PNi(CO)3 2063 1943

[CH3)3P]2 Ni(CO)2 1994 1934

The Change of the ligands causes some subtle changes which
affect the flow of the charge
 In cis (R3P)3Mo(CO)3 the stretching (F3P)3Mo(CO)3 2074 2026
frequency of the CO decreases with
electronegativity of the groups. (Cl3P)3Mo(CO)3 2041 1989
 An assumption that, phosphine
group is similar to carbonyl group in (C6H5PCl2)3Mo(CO)3 2016 1943
ability to donate and accept electrons
in metal complexes
[(C6H5)2PCl]3Mo(CO)3 1977 1885
 The ability to accept back donation
decreases in the order
 NO+ > CO > PF3 > AsCl3 > PCl3 > [(C6H5)3P]3Mo(CO)3 1949 835
As(OR) 3 > P(OR)3 > PR3
 Bridging carbonyl
 Consider the bonding of bridging CO and the metal. (sp2 hybridized) C-O is like a double
bond resembling that of ketone.
 Stretching frequency is lower than that of the terminal carbonyl in same or similar groups

 The Two metal atoms are donating  electrons rather than only one atom

 The frequency mainly occurs at 1700 - 1850 cm-1 (it behaves like organic keto group).
(terminal CO = 2125 – 1850 cm-1 ) behaving like aorganic Ketone ( indicates a C=O)
 Example
 In iridium carbonyl (Ir2(CO)8, the bridging carbonyl will show stretching frequency
between 1900 and 1650 cm-1
 Fe2 (CO)9 shows absorption bands at 2000 cm-1 (terminal carbonyl stretching) and 1830
cm-1 (bridging carbonyl stretching.
Carbonyl μ1cm-1 μ2cm-1 μ3cm-1

Rh2(CO)8 2060, 2084 1846, 1862

Rh4(CO)12 2044, 2070, 2074 1886

Rh6(CO)16 2945, 2075 1819

Uses of metal carbonyls

 Synthesis of other organic compounds

 Industrial processes:
❖ extraction and purification of nickel via a Ni(CO)4 to pure nickel (99% pure)
by the Mond process
❖ Catalysis catalyst precursors in homogeneous catalysis, such as
hydroformylation
❖ Hydrocarboxylation: the synthesis of acrylic acid and acrylic acid esters
❖ monsato Reaction: Production of acetic acid
❖ Potential CO releasing molecule (CO-RMs) in the drug industry where -CO
functions as a vasodilatory and an anti-inflammatory agent.
❖ Water–Gas Shift Reaction. Eg in the hydrogenation of quinoline
Study questions
1. Account for the following vibration frequencies in A and B groups
Group A
Ni(CO)4 2057 cm1
Fe(CO) 5 2034cm1
Cr(CO)6 1981 cm1

Group B
Ni(CO)4 2131 cm1
[(CH3)3P]Ni(CO)3 2063 cm1
[(CH3)3P]Ni(CO)2 1994 cm1
2. Define the following terms:
a) Isoelectronic b) Isolobal replacement c)Hapticity
c) Denticity