Chapter 5

LIGAND SUBSTITUTION REACTIONS

1. INTRODUCTION
The ligand substitution reactions play a fundamental role in organometallic
chemistry, because they are systematically involved in the syntheses of complexes
and in catalysis. As in organic chemistry, they can occur according to a “pairwise
process” or a single-electron-transfer mechanism involving radicals (paramagnetic
species). For each of these two categories, ligand substitution can occur
associatively or dissociatively, which corresponds respectively to the SN2 or SN1
mechanisms in organic chemistry. The analogy between these two fields continues
with the distinction, for single-electron-transfer mechanisms, to proceed according
to a chain- or non-chain mechanism. What distinguishes organometallic from
organic substitution reactions is the weakness of metal-ligand bonds compared to
the strength of most organic bonds. For instance, in 18-electron metal-carbonyl
complexes, despite their reputation of stability, the strength of metal-carbonyl bonds
is only from 25
kcal
·
mol–1 for [Ni(CO)4] to 46
kcal
·
mol–1 for [W(CO)6]. The
metal-carbonyl bond is in the average of metal-ligand bonds strength whose order is
the following: C5Me5 > Cp > C6Me6 > C6H6 > CO ~ PMe3 ~ C2H4 > PPh3 > Py >
CH3CN > THF ~ CH3COCH3.
The metal-cyclopentadienyl bond strength, for instance, reaches 118
kcal
·
mol–1 in
cobaltocenium, a very robust 18-electron complex.
In addition, the metal-ligand bonds tend to become stronger as one goes down in a
column of the periodic table. Finally, the strength of a metal-metal bond is of the
same order of magnitude as that of a metal-carbonyl bond.
We will successively examine the two pairwise mechanisms –
dissociative and
associative
– then those involving organometallic radicals.

2. “PAIRWISE” MECHANISMS
2.1. DISSOCIATIVE MECHANISM
The dissociative mechanism is that usually encountered for the ligand-substitution
reaction of 18-electron complexes.5.1,5.2
122 PART II – THE STOICHIOMETRIC REACTIONS OF TRANSITION-METAL COMPLEXES

A typical case is that of the reactions of metal-carbonyl complexes with phosphines

studied inter alia by Basolo.
k
Slow step: MLn MLn – 1 + L

Fast step: MLn – 1 + L’ MLn – 1 L’

The kinetics is of the type: rate
=
k
[MLn], as for organic SN1
reactions. The

activation energy is close to that of a M-L
bond (vide supra) and the enthalpy
variation is positive (
S‡ of the order of 10 to 15
eu), because the transition state is
less ordered than the initial one.
The stereochemistry of the reaction, observable when the starting complex has a
metal-centered chirality, can vary. Brunner has shown that, if the recombination
step is faster than the rearrangement of the 16-electron transition state or
intermediate, the reaction occurs with retention of configuration at the metal center.
In the opposite case, racemization is observed with the following mechanism (the
rate being inversely proportional to [PPh3], the dissociation of this ligand must be
involved):

25°C toluene
O Mn Mn
C PPh3 ON PPh3
NO C
Ph O
starting complex Ph

O Mn Mn O
C C
Ph ON ON Ph

The dissociative mechanism applies to the L
ligands, but not the X, LX or

L2X
ligands. The exchange of odd ligands only occurs if a Lewis acid such as AlCl3
or Ag+ able to abstract X–, LX– or L2X– is involved or if the reagent carries a
reactive anion (see section
3). The exchange of L
ligands can also be facilitated by
the presence of reagents such as Me3NO in the case where L
=
CO, but also using
various other means such as photochemistry, ultrasounds, microwaves (in the
context of the dissociative mechanism). Electrochemistry and other redox processes
involve electron-transfer mechanisms (vide infra). A practical technique that takes
advantage of the dissociative mechanism consists in preparing a complex containing
one or several labile ligands (see the bond strengths in section
1) such as NH3 or N2
or solvent molecules such as THF, CH3CN or CH3COCH3. These ligands are easily
substituted by other ligands according to the dissociative mechanism, because the
energies of their ligand-metal bonds are weak.