CHE 322

GROUP THEORY AND

ORGANOMETALLIC CHEMISTRY

Dr. N. Makuve
72919513
makuven@ub.ac.bw
Office 237/237

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 ASSESSMENT
• Test 1: Lab 247/140,141,142 & 259 on the 17th April 2024 from
18:00hrs to 20:00hrs.

• TEST 2: TBA

Tutorials and Self-tests will be on Moodle

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METAL CARBONYLS

• SYNTHESIS AND CHARACTERIZATION

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 CO CO CO
Metal carbonyls OC CO
CO
Ni OC Fe Cr
CO OC CO
OC CO
CO
CO CO

O
CO OC CO C CO
OC OC

OC Mn Mn CO OC Co Co CO
OC CO OC CO
CO OC C
O

CO
OC
CO CO
OC CO Ir
OC
CO Os CO OC CO
OC CO Ir Ir
OC CO
Os Os Ir CO
OC CO CO OC
OC CO
CO CO

Coordination number around the metal normally remains six or lesser.

17 electron species such as Mn(CO)5, Co(CO)4 dimerize to gain 18 electrons 8
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Homoleptic Carbonyl.

Compounds in which a metal is bonded with only carbonyl ligands are

called Homoleptic Carbonyl compounds.

For example, tetracarbonylnickle(0), pentacarbonyliron(0),

decacarbonyldimanganese(0)

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Polynuclear carbonyls contain two or more metal atoms, or
ions, in a single coordination sphere.
The two atoms may be held together through direct metal-metal
bonds, through bridging ligands, or both.

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 *
FOOD FOR THOUGHT
*
Why does CO bind a metal through its less LUMO

electronegative carbon atom than its more

2p
electronegative oxygen ? What makes it a 10.7 ev


good  acceptor ? HOMO

The highest occupied molecular orbital (HOMO) of CO is

2p
weakly antibonding (compared with the O atomic orbitals) 15.9 ev

and is an MO which is carbon based. Secondly, the * 

antibonding orbital which is the lowest unoccupied
molecular orbital (LUMO) is also of comparatively lower 2s *
19.5 ev
energy which makes it possible to interact with metal t2g
orbitals for  bonding. There exists a strong back bonding of  2s

metal electrons to the  * antibonding orbitals of CO C CO

32.4 ev
O

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 Infrared Spectroscopy- A spectro-analytical tool in chemistry

• The main goal of IR spectroscopic analysis is to determine the chemical functional groups in the

sample.

• Functional groups are identified based on vibrational modes of the groups such a stretching, bending

• Different vibrational modes absorb characteristic frequencies of IR radiation.

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 Infrared Spectroscopy- Spectra of Metal Carbonyls

The infrared spectroscopy can easily distinguish between terminal and

bridging binding modes of the metal carbonyl moiety.

O O
OC C C CO

OC Fe Fe CO bridging
OC C CO
O

terminal

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 Bridging and Terminal carbonyl
• The carbonyl ligand engages in a range of bonding modes in metal carbonyl
dimers and clusters. In the most common bridging mode, denoted μ2 or simply μ,
the CO ligand bridges a pair of metals. This bonding mode is observed in the
commonly available metal carbonyls: Co2(CO)8, Fe2(CO)9, Fe3(CO)12, and
Co4(CO)12

• Terminal carbonyl is bonded by chemical bonding to only one of the atoms in the
metal core of the cluster.

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 Terminal versus bridging carbonyls

O
M O
C
C
C M
M M M
O
M
terminal bridging  2 bridging 
 3
CO 2120-1850 cm-1
1850-1700 cm-1 1730-1620 cm-1

Cp
Fe CO
CO
OC CO OC Fe Cp
OC
Cr Fe
Cp
OC CO
CO Fe
Cp CO

2000 cm-1 2018, 1826 cm-1 1620 cm-1

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 Factors which affect CO stretching frequencies

1.Charge on the metal

2. Effect of other ligands

As the electron density on a metal centre increases, more -backbonding to

the CO ligand(s) takes place. This weakens the C–O bond further as more
electron density is pumped into the empty * anti-bonding carbonyl orbital.
This increases the M–C bond order and reduces the
C-O bond order. That is, the resonance structure M=C=O becomes more
dominant.

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 Effect of a ligands trans to CO
Effect of different co-ligands on CO (cm-1) of Mo(CO)3L3

Complex  CO cm–1
(fac isomers)
CO
Mo(CO)3(PF3)3 2090, 2055
L CO Mo(CO)3(PCl3)3 2040, 1991
Mo Mo(CO)3[P(OMe)3]3 1977, 1888
L CO
Mo(CO)3(PPh3)3 1934, 1835
L
Mo(CO)3(NCCH3)3 1915, 1783
Mo(CO)3(dien)* 1898, 1758
Mo(CO)3(Py)3 1888, 1746

With each negative charge added to the metal centre, the CO stretching frequency
decreases by approximately 100 cm–1.

The better the  donating capability of the other ligands on the metal, more electron
density given to the metal, more back bonding (electrons in the antibonding orbital of
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CO) and lower the CO stretching frequency.
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 Problem solving - synthesis

Give a scheme for the synthesis of Mn(CO)4(PPh3)[C(O)CH3]

starting from Manganese acetate, Mn(OAc)2.
high temp
2 Mn(OAc)2 + 4 Na + 10 CO high pressure Mn2(CO)10 + 4 NaOAc

Mn2(CO)10 + 2 Na 2 NaMn(CO)5

NaMn(CO)5 + CH3I CH3Mn(CO)5

CH3Mn(CO)5 + CO CH3C(O)Mn(CO)5 ( migratory insertion)
CH3C(O)Mn(CO)5 + PPh3 CH3C(O)Mn(CO)4PPh3
hv
Or at step 3 direct reaction with acyl chloride instead of MeI. Step 1 other
reducing agents e.g. AlEt3 can also be used.
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