Reactions, Kinetics and Mechanisms

Square Planar Complexes.

Consider two complexes, [PtCl4]-2 and [Pt(NH3)4]+2. If the

first were to react with two moles of NH3 and the second
H N

[
[

Cl

3
with two moles of Cl-, would these reactions
yield the
same
trans
Pt
Cl
NH3
product, [PtCl2(NH3)2]?

Cl

Cl

Pt

Cl

Cl

H3N

+NH3

NH3 +2
Pt

H3N

]
]
-2

NH3

-Cl-

-NH3
+Cl-

[
[

Cl
Cl

Cl

Pt
NH3

H3N
H3N

]
]
-1

NH3 +
Pt

Cl

+NH 3
-C l

Cl

NH3
Pt

Cl
H3N

NH3
Cl
Pt

-NH

Cl

NH3

+Cl -

Cl

NH3

Pt
Cl

cis
trans
cis

NH3

So, would predict that starting from either complex, should

Trans Effect

Note that in the second step, substitution always occurred

trans to one of the chlorines.
DEFINE: Trans Effect is the labilization of ligands trans to
other, trans-directing ligands:

CN- ~ CO > NO2- ~ SCN- ~ I- > Br- > Cl- > py > NH3 > OH- > H2O

By ordering the sequence of addition of substituents, can

use the trans effect to produce a desired isomer.

Cl
Cl

Pt

] [

Cl
+ NH-2
3

Cl

Cl

Cl

Cl
Pt

] [
-1 + Br -

NH3

Cl
Cl

Br
Pt

] [

Cl
+py

-1

py

NH3

+py

[ ]
Cl

Pt

Cl

Cl +-1
Br
py

[ ] [
Cl

Br

Pt

Cl

py

-1 + NH Cl
3
H3N

Br
Pt

py

Br
Pt
NH3

Explanations for the Trans Effect

1. Polarization Theory (Grinberg c. 1935).
in a completely symmetrical complex, such as [PtCl 4]-2 the
bond dipoles to the variousligands will be identical and will
L
cancel.

L M L

- L
however, if Lanother, more polarizing ligand (T) is introduced,
uncompensated dipole in
an additional
the
metal
will
+
L
M
T be
L M T introduced.
- L

the induced dipole in the metal will oppose the natural dipole

Explanations for the Trans Effect

2. Static -Bonding Theory.
two -bonding ligands will fight for the d-orbital electron
density of the metal.
L

T = stronger -bonder

more electron density

since there is less overlap between M and L, this bond will be

weaker. Therefore, -bonding ligand will be stronger transdirector.
Problem: this doesnt explains what happens when ligands are
-2
- ammonia.
-bonders,
example,
[Ptnot
X3T]
+ E for[PtX
rate = [PtX3T] [E]
2ET]

. Both mechanism might be used to explain the trans effect,

and do explain trends, however, these reactions have all
been found to be second order.

Mechanisms of Redox Reactions

At first glance it might appear that the mechanisms of

redox reactions would be trivial. That is, the two metals
approach each other, electron transfer takes place, and the
metals go on their way.
However, these reactions are complicated by the fact that
the metals are surrounded by ligands. This results in two
types of redox reactions:

1. Outer Sphere
in outer sphere reactions, the coordination sheres are not
altered.
e.g. [Fe(CN)6]-4 + [Mo(CN)8]-3 [Fe(CN)6]-3 + [Mo(CN)8]-4
in general, these reaction rates are faster because no bonds
are being broken.

Mechanisms of Redox Reactions

2. Inner Sphere.
here the ligand is intimately involved in electron
transfer.
[Co(NH
) Cl]+2 + [Cr(H O) ]+2
3 5

[(NH3)5CoClCr(H2O)5]+4 + H2O
[(NH3)5Co]+2 + [Cr(H2O)5Cl]+2

note that inner sphere reactions involve a physical

bridge by a ligand from one species to another during
the redox reaction.
evidence
for direct transfer:
if the reaction
is run in a
Frank-Condon
Principle:
the
solutionmotion
with radiolabeled
Cl-, little
of nuclei is very
slow or
as none of the
radiolabel is
found in to
theelectrons.
product.
compared

Consequences of Inner Sphere Reactions

1. Can get transfer of ligand; transferable ligand necessary,
but actual transfer is not. Note: bridging ligand must have
second, bond-forming, lone pair.
2. Rate can be no faster that the exchange rate of the ligand
in the absence of the redox reaction.
3. The rate determining step will be zero order in one of the
reactants.
if dissociation of ligand is rds, will be first order in that
species, but zero order in the other.
if rds is attack of second species, will be first order in it, zero
this species could
in the other.
not be synthesized

[(NH ) CoCN:]+2 + [Co(CN) ]-2

CoCNCo

3 5
any other
4. If
the bridging ligand5 has more than one atom, can
get way
different coordination of ligand (remote attack).
[(NH ) Co]+2 +
3 5

[CNCo(CN)
CoSCN:
+ Cr
CoSCNCr
5]
-3

Co

N
C
S

Cr

Kinetics of Octahedral Substitution.

There is not enough data to form a continuous series, but

metal ions can be put into four classes based on waterexchange rates.

1. Extremely Fast; k 108 sec-1

e.g. alkalai metals and larger alkaline earths

2. Fast; k 105 to 108 sec-1

e.g. dipositive transition metals and tripositive lanthanides

3. Relatively slow; k 1 to 104 sec-1

e.g. most of the tripositive transition metals, Be+2 and Al+3

4. Slow (kinetically inert); k 10-1 to 10-9 sec-1

e.g. Cr+3 (d3); Co+3 (l.s. d6); Pt+2 (l.s. d8); Rh+2; Ru+2
note: these metals are inert because they have very high
LFSE and either half or filled subshells; any perturbation
would cause crystal field to become less stable.

. Q: Why would tripositive metal ions be more stable than

Octahedral Ligand Substitution Reactions

Coordination Sphere Theory

It is easier to understand Oh
reactions if we look at what is
going on around the metal in
terms of coordination spheres.

1st sphere: coordinated ligands (L).

2nd sphere: solvent and other

molecules (X) held nearby via
hydrogen bonds/polar interactions
(much weaker than 1st sphere).

3rd sphere: balance of solvent (V).

Substitution in Oh complexes is an
exchange of species between the

Two Substitution Reaction Types

1. Solvolysis: substitution of a ligand by solvent.
L
L

L
M
L

L*
+X
L

L
M
L

X
L

+ L*

2. Anation: replacement of coordinated solvent.

L
L

L
M
L

L
X+ L
L

L
M
L

L
L

+X

. Notice that there is NOT direct substitution of one anion

for another.
. Instead, Oh complex first loses a coordinated anion by
solvolysis, then the newly coordinated
solvent is relaced by
+H2O
+Cl+2
+3
another
anion
in an[Lanation
reaction.
[L5CoBr]
[L5CoCl]+2
5CoOH2]
solvolysis

anation

Two Possible Mechanisms

Associative (SN2)
slow

[N5ML] + E
leaving

entering

[N5ME] + L

7-coordinate

Dissociative (SN1)
slow
fast
[N5ML]
[N5M] + E
-L

fast

[N5MLE]

5-coordinate

[N5ME]

How could one determine experimentally whether the

reaction is Associative or Dissociative?
Answer: Determine the rate law.
if Associative: rate = k [N5ML] [E]
if Dissociative: rate = k [N5ML]

initial concentration
of E will not affect
the rate.

Two Possible Mechanisms

~8 order of magnitude difference in rates.

difference in rates less than 2x.

These data indicate a dissociative mechanism. In fact,

rates correlate well with Co-L bond strengths indicating
that this bond is broken initially (i.e. the weaker the bond,
the greater the value of k).
NOTE: Although you might expect to see a trans-effect in
Oh complexes, THERE IS NONE! (i.e. dont apply square
planar rules here)

Template Effect
method for producing macrocyclic ligands.

however, if throw in a metal.

the metal is holding the reactants together in required
orientation.
the metal holds sulfurs in correct position to allow reaction
with both Brs.
Can not do this without metal; get polymer
cant even make starting material without the metal.