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Lecture 1 Organometallics

This document provides an introduction to organometallic chemistry. It defines organometallic compounds as those containing direct metal-carbon bonds. Common examples like ferrocene are shown. Carbon monoxide is discussed as an important ligand that stabilizes low oxidation state metals. The 18-electron rule for predicting structures of metal carbonyl complexes is explained through examples like Cr(CO)6. Synthesis of metal carbonyls from carbon monoxide and various metal precursors is also covered.

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328 views

Lecture 1 Organometallics

This document provides an introduction to organometallic chemistry. It defines organometallic compounds as those containing direct metal-carbon bonds. Common examples like ferrocene are shown. Carbon monoxide is discussed as an important ligand that stabilizes low oxidation state metals. The 18-electron rule for predicting structures of metal carbonyl complexes is explained through examples like Cr(CO)6. Synthesis of metal carbonyls from carbon monoxide and various metal precursors is also covered.

Uploaded by

A J
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPT, PDF, TXT or read online on Scribd
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Organometallic

Chemistry
CHEM 20312
Dr. Mark Whiteley 4.02g
[email protected]
Office Hour (weeks 9-12) Wednesday
9.00am
1

Recommended Texts
M Bochmann, 'Organometallics 1',
Oxford Chemistry Primers, No. 12.
M Bochmann, 'Organometallics 2',
Oxford Chemistry Primers, No. 13.
C. Elschenbroich, 'Organometallics',
2nd or 3rd eds, VCH.
Housecroft and Sharpe 4th Edition
Chapters 24 and 25
2

What defines an Organometallic Complex?

[Fe(-C5H5)2]

Ferrocene

[RhI2(CO)2]-

[As2(CH3
)4]

They ALL have a DIRECT metal carbon bond


3

Definition of Organometallic
Compounds
Organometallic chemistry: chemistry of
molecules containing Metal-Carbon
bonds.
This course considers d-block (transition)
metals but main group organometallics
of Li, Mg (Grignard) Hg and Sn also very
important synthetic reagents.
M is often in low oxidation state (+2, +1,
0 or even negative), hence electron-rich.
Stabilised by electron-acceptor ligands.
4

Importance of Organometallic
Chemistry:
(i) Catalysis
Monsanto process:
MeOH/CO/ Rh cat.
MeCO2H (acetic acid)
Hydroformylation:
RCH=CH2 / CO/H2/ Rh cat.
RCH2CH2CHO
(aldehyde)
Ziegler-Natta process:
CH2=CH2 Ti cat.
polyethylene
All work because the organic molecules are
coordinated and activated by the metal catalyst.
Homogeneous systems have advantages of mild
operating conditions and high product specificity.
5

(ii) Organic Synthesis:

1. Isolation of reactive organic


molecules as metal-coordinated
species
eg. carbene, cyclobutadiene.
2. Reactivity modification via transition
metal coordination
eg activation of alkenes and arenes to
nucleophilic addition.
6

Metal Carbonyl Complexes M(CO)n

Carbon Monoxide (CO) acts as a good ligand to


d-block transition metals.

The CO ligand has zero formal charge and


donates an electron pair (2 electrons) to the
metal centre.
CO acts as a strong -acceptor ligand and
therefore stabilises complexes with metals in a
low oxidation state
Metal carbonyl complexes are important as
starting materials for a wide range of
organometallic complexes via ligand
substitution reactions
7

Synthesis of Metal Carbonyl


Complexes
1. Direct reaction of CO with the metal powder

Ni +
CO

1 atmosphere CO, 25C

Ni(CO)4

100 atmosphere (bar) CO, 150C


Fe(CO)5
Fe + CO

2. Reduction of a metal halide in a CO atmosphere


VCl3

Diglyme, 300 bar


+ 3Na + CO

[V(CO)6]

Diglyme =
Di(2-methoxyethyl) ether

Benzene
WCl6 + 2Et3Al + CO
W(CO)6
70 bar, 50C

Structures of first row d block (3d)


homoleptic metal carbonyls

Bridging
2-CO

Terminal CO
10

Trends in metal carbonyl


structures
The 18-electron rule

Cr group 6
Cr(0) d6

Fe group 8 Ni group 10
Fe(0) d8
Ni(0) d10

6 CO = 12 e5 CO = 10 e4 CO = 8 e
Total 18 e Total 18 e Total 18 e
11

The 18-electron rule


Metal valence d electrons + ligand
electrons donated to metal sum to 18
(filled s, p and d orbitals on metal)
Applies to complexes with good
acceptor ligands (eg CO)
Some exceptions especially 17- and
16- electron systems (see later).
Can be used to predict structures of
organometallics.

12

Examples of electron counting:


1. Cr(CO)6
Group

Number of e-

Cr0

CO x 6

12

Total

18

13

2. Mn2(CO)10 (Metal-metal
bonding)
(Mn d7 has an uneven (odd) number of
valence d electrons)
Mn0

CO x 5

10

Mn Mn

Total

18

Formation of a Mn-Mn
metal-metal bond adds an extra
electron to the count at each metal

14

3. Fe2(CO)9 (Bridging carbonyl


ligands)
Fe0

Terminal CO

Bridging CO

COterminal x 3

8
6

CObridging x 3

MM

Total

18

2-bridging CO ligands provide 1 electron to each metal centre.


Bridging CO usually observed for smaller metal centres:
(i) First row (3d) metals (ii) metals on right hand side of d block eg
15
Co not Mn

4. Na[Mn(CO)5] (Charged species)


-

O
C
OC
O

Mn

C
C
O

CO

Mn

CO x 5

10

negative
charge

Total

18

In Na[Mn(CO)5] the anion [Mn(CO)5] is present.


Count by adding one extra electron for the negative
charge.
16

5. [V(CO)6] (An anomalous case)


v

O
C
OC
O

C
C
O

CO x 6
Total

5
12
17

V(CO)6 is a 17-electron radical (has an unpaired


electron and does not obey the 18-electron rule).
Readily reduced to 18-electron [V(CO)6]
V-V bonded bimetallic not formed
17

6. [Ru3(CO)12] (A metal cluster)


O

O
C
Ru
C
O

C
Ru

OC
OC

O
C
CO
O
C

C
O

CO

Ru
C
O

Ru

CO x 4
Ru-Ru x 2

8
2

Total
O

18

Metal cluster: more than 2 metals in complex


Ru group 8 (like Fe) d8
All CO terminal (larger 4d metal reduces
possibility of bridging)
18

7. Mo(CO)n (Use of the 18-electron rule


to predict molecular formula)
Mo is a group 6 metal (like Cr)
Mo(0) d6
Mo(CO)n obeys 18-electron rule. Each
CO provides 2 electrons to Mo
6 (Mo) + n x 2 = 18
n = 6. Formula is Mo(CO)6

19

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