Organometallic Chemistry

an overview of structures and reactions

Peter H.M. Budzelaar

 Between organic and inorganic...

Organic chemistry:
• more or less covalent C-X bonds
• rigid element environments
• fixed oxidation states (better: valencies)

??Organometallic chemistry??

Inorganic chemistry:
• primarily ionic M-X bonds, dative M-L bonds
• variable and often fluxional environments
• variable oxidation states

2 Overview of Organometallic Chemistry

 Organometallic reactivity

Since most organometallics are intermediates, the focus in

organometallic chemistry is usually on understanding and tuning
reactivity

This starts with analyzing reaction mechanisms in terms of

elementary steps

The number of possible elementary steps is larger than in

"pure organic" chemistry, but the ideas are similar

3 Overview of Organometallic Chemistry

 Organometallic structures

Knowledge of inorganic and coordination chemistry is useful to

understand geometries, electron counts and oxidation states of
organometallic compounds

Organometallics are more covalent and often less symmetric

than coordination compounds, so orbital symmetry arguments
are not as important

4 Overview of Organometallic Chemistry

Trends in organometallic chemistry

Organometallic chemistry is concerned with all metals, in

combination with all "organic" elements.
there are many metals !

Generalization is important
the chemistry of e.g. Fe is not much more complicated
than that of C, but after that there are 80 more metals...
we divide reactions in broader categories than organic chemists do

We concentrate on the M side of the M-C bond,

and on how to tune its reactivity

5 Overview of Organometallic Chemistry

 Elements of interest

Organic elements
Main group metals
Transition metals

6 Overview of Organometallic Chemistry

 Organic vs organometallic reactivity

-X Y
Organic chemistry: X SN1 int (6-e)
C-C / C-H : nearly covalent
C+-X- : polar (partly ionic)
X Y
reactivity dominated by nucleophilic attack at C
Y -X
SN2 and SN1 like reactivity
Y
SN2 TS (10-e ?)
Organometallic chemistry:
C is the negative end of the M-C bond ("umpolung")
reactivity dominated by electrophilic attack at C
or nucleophilic attack at M dissociative
associative and dissociative substitution at M - C H (C2H4)PdCl2
2 4 CO
(C2H4)2PdCl2 (C2H4)(CO)PdCl2
?
CO - C2H4
(C2H4)2(CO)PdCl2
associative

7 Overview of Organometallic Chemistry

 Main-group organometallics
Me
s and p orbitals. Me Me
Al Al
8-e rule, usually.
Me Me 8-e
Me
with a lot of exceptions

Cl 10-e
Cl
Me Sn Me
More electropositive and larger:
higher coordination numbers, O
regardless of the number of electrons. N

“Early" groups and not very electropositive:

lower coordination numbers. Me Zn Me
4-e

8 Overview of Organometallic Chemistry

 Main-group organometallics

Metal is the "+" side of the M-C bond.

Chemistry dominated by nucleophilic attack of C- at electrophiles.
this is also the main application in organic synthesis

MeMgBr + Me2CO Me3COMgBr

note: this is a simplified picture

of the Grignard reaction

9 Overview of Organometallic Chemistry

 Main-group organometallics

M-M multiple bonds are fairly weak and rather reactive

they are a curiosity and relatively unimportant,
certainly compared to C-C multiple bonds
Bond strengths in kcal/mol:
C-C 85 C=C 150
N-N 40 N=N 100
P-P 50 P=P 75
Multiple-bonded compounds often have unusual geometries
"Me4Sn2"
Me4C2

10 Overview of Organometallic Chemistry

 Transition-metal organometallics

s, p and d orbitals
18-e rule, sometimes 16-e Ni
other counts relatively rare
CO
OC CO 18-e
Cr
OC CO
Fe Et3P Me
CO 18-e Pt
Et3P Cl
18-e
16-e

11 Overview of Organometallic Chemistry

 Transition-metal organometallics

Lower electron counts if metals are sterically saturated:

nor Me
nor Me
Co
Me W
nor Me
nor Me Me
12-e
nor =

13-e

Ti Me
Me

16-e

12 Overview of Organometallic Chemistry

 Transition-metal organometallics

Often ligands capable of donating 2-8 electrons

Preference for -system ligands (good overlap with d-orbitals)

carbene cyclopentadienyl
O
olefin allyl
C C

2e 2e 2e 3e 5e

Bonding to neutral ligands (olefin/diene/CO/phosphine)

relatively weak
Important for catalysis!

13 Overview of Organometallic Chemistry

 Transition-metal organometallics

An olefin complex: (Acac)Ir(NCMe)(C2H4)

donation

backdonation

14 Overview of Organometallic Chemistry

 Transition-metal organometallics

“Forbidden” reactions ?
?
+

Mo Mo
+

No symmetry
Very fast

Symmetry-forbidden
Does not happen

15 Overview of Organometallic Chemistry

 Reactivity of the M-C bond

Polar  reactive towards e.g.

• Water: M-OH + H-C

Me3Al explodes with water; Me4Sn does not react.

• Oxygen: M-O-O-C
Me2Zn inflames in air; Me4Ge does not react.

M-O-C C
• Carbonyl groups:
MeLi adds at -80°C, Me3Sb not even at +50°C.

16 Overview of Organometallic Chemistry

 Reactivity of the M-C bond

Oxidation and hydrolysis: large driving force

Bond strengths in kcal/mol:

Al-C 65 As-C 55 Si-C 74
Al-O 119 As-O 72 Si-O 108
Al-Cl 100 Si-Cl 91

17 Overview of Organometallic Chemistry

 Organometallic reaction steps

Ligand dissociation / coordination

Me3Al + NMe3 Me3Al-NMe3

note: free Me3Al
6e 8e
dimerizes to Me6Al2

Mo(CO)6 Mo(CO)5 + CO
18e 16e

18 Overview of Organometallic Chemistry

 Organometallic reaction steps

Insertion and -elimination

MeMgBr + MeC N Me2C=NMgBr

N N N
N Fe Me N Fe Me N Fe
N N N
Me

N +
N Fe Me =
N
N
N Fe N
Ar =
Ar Ar

19 Overview of Organometallic Chemistry

 Organometallic reaction steps

Insertion and -elimination P P

P Pd P Pd
H
H

P P = Ph2P PPh2

20 Overview of Organometallic Chemistry

 Organometallic reaction steps

Oxidative addition / Reductive elimination H

P Cl H2 P H
Rh Rh "P" = PPh3
P P P P
Cl

21 Overview of Organometallic Chemistry

 Organometallic reaction steps
Oxidative addition / Reductive elimination
Me
O L
Rh L = P(OPh)3
O L
O I
L MeI
Rh L
O L O I
Rh L = PPh3
O Me
L

22 Overview of Organometallic Chemistry

 Organometallic reaction steps

-bond metathesis H3
*CH4 *C
Lu CH3 Lu H Lu *CH3
C
H3

14 e

23 Overview of Organometallic Chemistry

 Organometallic reaction steps

Redox reactions

- e-
Fe Fe

Homolysis
Et Hg Et Et Hg + Et

24 Overview of Organometallic Chemistry

 Organometallic reaction steps

Reactivity of coordinated ligands

25 Overview of Organometallic Chemistry

Factors governing structure and reactivity
of organometallic compounds

• M-C, M-X bond strengths

• Electronegativity of M (polarity of M-C etc bonds)

• Number of (d) electrons

• Coordination number

• Steric hindrance

26 Overview of Organometallic Chemistry

 Trends in the periodic table

Main group metals:

• left and down: more electropositive
• down: higher oxidation states less stable

Transition metals:
• middle: strongest preference for 18-e
• 2nd and 3rd row: strong preference for
paired electrons (low-spin states)
• down: higher oxidation states more stable

27 Overview of Organometallic Chemistry

 Working with organometallics

Synthesis and reactivity studies (inert atmosphere!):

• Glove box
• Schlenk line, specialized glassware

Characterization:
• Xray diffraction  structure  bonding
• NMR  structure en dynamic behaviour
• (calculations)

• IR Not:
• MS • GC
• EPR • LC

28 Overview of Organometallic Chemistry