c
c
Introduction
ï The products of substitution reactions of
square-planar complexes [O
O
O
O
have
the same configuration as the reactants,
with direct replacement of the departing
ligand by the new ligand.
ï The rates vary enormously, and different
compounds can be formed, depending both
on the entering and the leaving ligands.
inetics and Stereochemistry of
Square Planar Substitutions
Square-planar substitution reactions frequently
show two term rate laws, of the form :
!" # ! $!
where:
$!is concentration of the incoming ligand
Both pathways (both terms in the rate law) are
considered to be associative, in spite of the
difference in order.
The Ñ term easily fits an associative mechanism
in which the incoming ligand Y and the reacting
complex form a 5-coordinate transition state.
The accepted explanation for the Ñ term is a
solvent-assisted reaction, with solvent replacing
X on the complex through a similar 5-
coordinate transition state, and then itself
being replaced by Y.
The second step of this mechanism is presumed
to be faster than the first, and the
concentration of solvent is large and
unchanging, so the overall rate law for this path
is first order in complex.
It is generally accepted that reactions of
square-planar compounds are associative,
although there is doubt about the degree of
association, and they are classified as
The incoming ligand approaches along the z axis. As it
bonds to the Pt, the complex rearranges to approximate
a trigonal bipyramid with Pt, T, X, and Y in the trigonal
plane. As X leaves, Y moves down into the plane of T, Pt,
and the two L ligands.
This same general description will fit whether the
incoming ligand bonds strongly to Pt before the
departing ligand bond is weakened appreciably (la)
or the departing ligand bond is weakened
considerably before the incoming ligand forms its
bond
The solvent-assisted mechanism follows the same pattern
but requires two associative steps for completion.
This mechanism explains naturally the effect of the
incoming ligand. !
. Pt(II) is generally a soft
acid, so soft ligands react more readily with it. The
order of ligand reactivity depends somewhat on the
other ligands on the Pt, but the order for the
reaction :
%## "$
%#$ "%
for different Y in methanol was found to be as
follows :
& '(% 'c(% '')% '(&% '(*#% ' '(+&,% '
+&*+
Veactants with ligands other than chloride as T is found
in a similar order, with some shuffling of the center of
the list. The ratio of the rate constants for the extremes
in the list is very large, with k(PPh3)/k(CH3OH) = 9 x 108.
Because T and Y have similar positions in the transition
state, it is reasonable for them to have similar effects on
the rate, and they do.
By the same argument, the leaving group X should also
have a significant influence on the rate, and it does. The
order of ligands is nearly the reverse of that G
above,
with hard ligands such as Cl-, NH&, and NO&% leaving
quickly, while soft ligands with considerable ʋ bonding
such as CN- and NO#% leave reluctantly.
¢
¢
The rate increases by a factor of 105 with H20 as
compared with X- = CN- or NO2 as the leaving
group. The bond-strengthening effect of the metal-
to-ligand ʋ bonding
of these
ligands significantly.
In addition, ʋ bonding to the leaving group uses the
same orbitals as those bonding to the entering
group in the trigonal plane.
These two effects result in the slow displacement of
metal-to-ligand- ʋ bonding ligands when compared
with ligands with only ʍ bonding or ligand-to-metal
ʋ bonding.
`ood leaving groups (those that leave easily)
show little discrimination between entering
groups. Apparently, the ease of breaking the Pt
Ͷ X bond takes precedence over the formation
of the Pt Ͷ Y bond.
On the other hand, for complexes with less
reactive leaving groups, the other ligands have
a significant role; the softer PEt3 and AsEt3
ligands show a large selective effect when
compared with the harder dien or en ligands.
The O Effect
In 1926, Chernyaev introduced the concept of
the
effect in platinum chemistry.
In reactions of square-planar Pt(II) compounds,
ligands
to chloride are more easily
replaced than those
to ligands such as
ammonia; chloride is said to have a stronger
effect than ammonia.
When coupled with the fact that chloride itself
is more easily replaced than ammonia, this
effect allows the formation of isomeric Pt
compounds.
In reaction (a), after the first ammonia is replaced, the
second replacement is trans to the first CI-. In reaction
(b), the second replacement is trans to Cl- (replacement
of ammonia in the second reaction is possible, but then
the reactant and product are identical).
The first steps in reactions (c) through (f) are the possible
replacements, with nearly equal probabilities for
replacement of NH3 or py in any position. The second
steps of (c) through (f) depend on the trans effect of Cl-.
Both steps of (g) and (h) depend on the greater lability of
Cl-.
By using reactions such as these, it is possible to
prepare specific isomers with different ligands.
Chernyaev and coworkers did much of this,
preparing a wide variety of compounds and
establishing the order of
effect ligands:
(% ,*,#+- '+& ,c+# '(*#% '.% ')% '%
'(+& , '*+% '+#*
ï c/
%/
Two factors dominate the explanations of the
effect, weakening of the Pt Ͷ X bond and stabilization of
the presumed 5-coordinate transition state. The energy
relationships are given in figure below, with the
activation energy the difference between the reactant
ground state and the first transition state.
(a) Poor trans effect, low ground state, high transition
state. (b) ʍ-Bonding effect, higher ground state (trans
influence). (c) ʋ-Bonding effect, lower transition state,
(trans effect).
This ground state effect is
sometimes called the
and applies
primarily to the leaving group.
It is a thermodynamic effect,
contributing to the overall
kinetic result by changing the
reactant ground state.
The Pt Ͷ X bond is influenced by the Pt ͶT bond,
because both use the O
and orbitals. When
the Pt ͶT ʍ-bond is strong, it uses a larger part of these
orbitals and leaves less for the Pt ͶX bond. As a result,
the PtͶX bond is weaker and its ground state (ʍ -
bonding orbital) is higher in energy, leading to a smaller
activation energy for the breaking of this bond [figure b.
This part of the explanation predicts the order
for the
effect based on the relative ʍ-
donor properties of the ligands:
+% '& 'c(% '.% ,+&% ,*,(% ')% ''
(+& '*+%
The order given here is not quite correct for the
effect, particularly for CO and CN-, which
have strong
effects.
ï %/
The additional factor needed is ʋ bonding in the PtͶ T
bond. When the T ligand forms a strong ʋ-acceptor bond
with Pt, charge is removed from Pt and the entrance of
another ligand to form a 5-coordinate species is more
likely. In addition to the charge effect, the
orbital, which is involved in ʍ bonding in the square-
planar geometry, and both the and orbitals can
contribute to ʋ bonding in the trigonal-bipyramidal
transition state.
Here, the effect on the ground state of the reactant is
small, but the energy of the transition state is lowered,
again reducing the activation energy [figure c. The order
of ʋ-acceptor ability of the ligands is :
#+- ,*'(% '(*#% 'c('.% ')% '% '(+& '*+%
The expanded overall
effect list is then the
result of the combination of the two effects:
Ligands highest in the series are strong ʋ
acceptors, followed by strong ʍ-donors.
Ligands at the low end of the series have neither
strong ʍ-donor nor ʋ-acceptor abilities.
The
effect can be very G
rates may differ
as much as 106 between complexes with strong
effect ligands and those with weak
effect ligands.
Exercise
ï It is possible to prepare different isomers of
Pt(II) complexes with four different ligands.
Predict the products expected if 1 mole of
[PtCl42- is reacted successively with the
following reagent (
G
O
):
a. 2 moles of ammonia
b. 2 moles of pyridine
c. 2 moles of chloride
d. 1 mole of nitrite, NO2-
