Reactions mechanisms of

Coordination Chemistry of
d-orbital Complexes

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 Why study reaction mechanisms?
• We will examine the mechanisms of both
substitution and redox processes in transition
metal complexes
• Provides insight into how mechanisms are
studied
• Provides understanding that can used to design
synthetic pathways to new compounds
• Provides understanding that can be used to
optimize performance of catalysts etc.
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 Introduction
Reactions of coordination compounds
share some characteristics with
reactions of other molecules, both
organic and inorganic, so an
understanding of coordination
compound reactions can draw on
some familiar concepts.

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The chemistry of coordination compounds
has some additional features because the
molecules have more complex geometries and
more possibilities for rearrangement, the
metal atoms exhibit more variability in their
reactions, and different factors influence the
course of reactions.
The goal of those studying reaction kinetics and mechanisms is
to understand the electronic structure of the compounds and their
interactions.
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Types of reaction
in coordination complexes
The methods used in synthesizing coordination
compounds often include some combination of :
1. Substitution reactions :
- dissociative substitution (SN 1)
- associative substitution (SN 2)
- interchange
2. Redox reaction
- inner sphere
- outer sphere
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Dissociative reaction (D): loss of a ligand to form an
intermediate with a lower coordination number is followed by
addition of a new ligand to the intermediate
Associative reaction (A): the incoming ligand adds to the
complex and a discernible intermediate with an increased
coordination number is formed. It is followed by a faster reaction
in which the leaving ligand is lost
Interchange reaction (I): the incoming ligand is presumed to
assist in the reaction but no detectable intermediate appear
Dissociative Interchange (Id): the reactions is primarily
dissociation and the degree of assistance is small

Associative Interchange (Ia): when the incoming ligand begins

forming a bond to the central atom before the departing ligand is
weakened appreciably
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 Mechanism of ligand exchange reactions
in octahedral complexes
MLnX + Y MLnY + X

Dissociative (D) Associative (A)

M Ln X M Ln Y M Ln X M Ln Y

X M Ln Y Y X
M Ln XY

Interchange (I)
M Ln X M Ln Y

Y X
[M Ln]°

Ia if association X Y
Id if dissociation
is more important is more important
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 L

L
L M
L
L
L
L
L L
L L Trigonal bipyramidal, 5 CN
M
M
L L
L L
L
Y
X
L L
octahedral
M
L L
Square pyramidal, 5 CN

Intermediates

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 Kinetics
of dissociative reactions

If the [intermediate] <<<<

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Associative reaction (A) for Octahedral:
X Y
X Y
L L L L L L
M M M
L L L L L L
L L Intermediate, 7 CN L

Kinetics of associative reactions

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Principal mechanisms of ligand exchange in octahedral complexes

Dissociative

Associative

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 Dissociative pathway
(5-coordinated intermediate)

MOST COMMON

Associative pathway
(7-coordinated intermediate)

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 Reaction Profiles

dissociative interchange associative

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 Kinetics
of interchange reactions Fast equilibrium
K1 = k1/k-1

k2 << k-1

For [Y] >> [ML5X]

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 Experimental evidence for dissociative mechanisms

Rate is independent of the nature of L

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Experimental evidence for Associative mechanisms

Rate is dependent on the nature of L

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 Substitution reactions in square-planar complexes
And the trans effect

L X L Y
-X,+Y
+X, -Y
M M
T L T L

(the ability of T to labilize X)

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Mechanisms of ligand exchange reactions
in square planar complexes

L L S
M +S
L X L L
Initial complex
M
+Y L X

-X
Y
L L L L
M -d[ML 3X]/dt = (ks + ky [Y]) [ML 3X] M
L X L S
+Y

Y
L L
-X M
L S
L L
M -S
L Y
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Cis and trans were found as the results of
square planar substitution

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The trans effect H3N Cl
+NH3
Pt
-2 - -Cl-

Cl Cl Cl Cl NH3
Cl
+NH3
trans, not found
Pt -Cl- Pt
NH3 Cl NH3
Cl Cl Cl
+NH3
Pt
-Cl-

Cl NH3

cis, the exclusive

+2 +1 product
H3N NH3 H3N NH3
+Cl- Cl NH3
Pt +Cl- Pt
-NH3
-NH3 Pt
H3N NH3 H3N Cl
H3N Cl

trans, the exclusive

product

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The trans effect in synthesis
-2 - -
Cl Cl Cl Cl Cl- Br
+NH3 +Br-
Pt -Cl- Pt -Cl- Pt
Cl Cl NH3 NH3
Cl Cl

Trans effect can

Cl- Br
be used to first isomer
produce the Pt
desired isomer py NH3

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The trans effect in synthesis
-2 - -
Cl Cl Cl Cl Cl- Br
+ py +Br-
Pt -Cl- Pt -Cl- Pt
Cl Cl py py
Cl Cl

Cl- Br second isomer

Pt
H3N py

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The trans effect in synthesis
-2 +
Cl Cl Cl NH3 Cl NH3
+2NH3 +py
Pt -Cl- Pt -Cl- Pt
Cl Cl Cl NH3 py NH3

By ordering the sequence of

addition of substituents , the Cl NH3
trans effect may utilized to Pt
provide the desired isomer third isomer
py Br

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An interesting application of trans effect is in distinguishing
between cis and trans isomer of complexes type [PtA2X2]

+ +
Cl NH3 Cl Cl tu
+ tu NH3 + tu
Pt -Cl- Pt -NH3 Pt
Cl NH3 tu tu NH3
NH3

cis

+ +
tu tu tu tu
+ tu
Pt -NH3 Pt
tu tu tu NH3

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Addition of thiourea (tu) to the cis complex result in complete
replacement of the former ligands

But in trans isomer the replacement stop after the two halide
ions replaced since the trans ammonia molecules do not
labilize each other

+ +
Cl NH3 Cl tu NH3
+ tu NH3 + tu
Pt -Cl- Pt -NH3 Pt
H3N Cl tu H3N tu
H3N

trans

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 Synthetic applications of the trans effect

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 Synthetic applications of the trans effect

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 the trans effect must be controlled kinetically
since the thermodynamically most stable isomer
is not always produced

Isomer is
formed
depending on
the reaction
sequence

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 MECHANISM OF THE TRANS EFFECT
Two viewpoints have been advanced with respect to the
mechanism of the trans effect
1. Weakening of trans bond
2. Lowering of the activation energy of trans replacement
Trans effect is defined as the effect of coordinated group [T]
upon the rate of substitution reaction of ligand opposite to it
-2 -2 -2
Cl Cl T Cl T Cl
+T +T
Pt -Cl- Pt -Cl- Pt
Cl Cl Cl Cl Cl T

In contras, the trans influence defined as the extent to which that

ligand weakens the bonds trans
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1. The polarization theory of Grinberg
• For completely symmetrical complex such as [PtCl4]-2the
bond dipole to various ligands will be identical. In contras
if a more polarizable and polarizing ligand, T, ( such as I-)
is introduced, its polarizability will induced an additional,
uncompensated dipole in metal. This induced dipole in
metal will oppose the natural dipole of ligand trans to the
polarizing ligand
• This theory supported by the following facts :
- it should be important when the central metal atom is
large and polarizable, Pt+2 > Pd+2 > Ni+2
- the trans directing groups are more polarizable
either because they are large ( I-) or multiply bonded (en,
CN-, CO) + +
N trans effect operating N
- -
+ N - + - N+
-
+ T - + - - L+
N
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No trans effect
-
+ N
+
 2. π-bonding theory
A second approach that involves the weakening of the trans
bond is the static pi-bonding theory
- two pi-bonding ligands vying for the d orbital of metal
atom will tending to labilize each other
-the stronger pi bonder dominate, weakening the bonding of
group trans to it

T M X

pi-bonding, pi-bonding,
strong weak

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3. Cadwell theory

• Related to the polarization theory of Grynberg

• The trans effect can be explained in term of the
electronegativity of substituents
• Most electronegative substituents will tend to assume axial
positions in such a trigonal bipyramid
• Loss of the leaving group L from the transition state will
re-form the square complex with the entering group E,
trans to the least electronegative group T
N
E N
N +E -L E
L T T
T
L N
N
N intermediate

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4. Cadtt and Orgel theory
• assumed a trigonal bipyramidal intermediate or activated
complex
• Proposed that a pi-bonding ligand would stabilize such as
intermediate
• Suggested that a strong pi-bonding ligand would remove
electron density from metal through back-bonding
• Hence the more positive metal could more ready accept the
entering, fifth ligand
N E

E
T M T M
L
N
Back bonding L
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 Activation Energy and the trans Effect.

Sigma-bonding effects

The depth of the energy curve for the intermediate and the relative heights
of the two maxima will vary with the specific reaction. (a) Poor trans effect,
low ground state, high transition state. (b) a-Bonding effect, higher ground
state (trans influence). (c) n-Bonding effect, lower transition state, (trans
effect).

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The Pt-X bond is influenced by the Pt-T bond, because both
use the Pt p, and dx2-y2 orbitals. When the Pt-T σ bond is strong,
it uses a larger part of these orbitals and leaves less for the Pt -
X bond. As a result, the Pt-X bond is weaker and its ground
state (sigma-bonding orbital) is higher in energy, leading to a
smaller activation energy for the breaking of this bond

The order of trans effect of the ligands is

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 SUBSTITUTION IN OCTAHEDRAL COMPLEXES

• Substitution in octahedral complexes take place via

dissociative and associative mechanism
• Many of them go via dissociative mechanism
• One might expect the trans effect to be operable in
octahedral complexes as well as square planar complexes
• Evidence for its presence in octahedral is not abundant
• For [Co(NH3)5X]2+ complexes, there is definite evidence
for the trans influence
• In metal carbonyls the trans effect seem to be operative if
the carbonyls group and the in coming ligand trans to each
other

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 Trans-Effect in
Octahedral Complexes

Co Co

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Substitution in Co(III) complexes

• The best studied systems because of their stability and

availability
• The trans effect is not shown
• Substitution reactions occur via a dissociative
mechanism (D or SN 1)
• Interchange mechanism tending toward the dissociative
side (Id)
Dissociative mechanism
-L- +E-
[N5 CoL]+n →
slow [CoN5 ]+n+1 →
fast
[N5CoE]+n

Interchange mechanism
+E- -L-
[N5 CoL]+n →
slow [N5 CoL]+nE →
slow [N5 CoE]+n → [N5CoE]+n
L fast

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• Thermodynamically, the Co-L bond is broken initially. The
bond between the metal and an anion would be broken
readily if electron density were increased on the metal
• Electron donating ligands should therefore assist
replacement of L
• This proves to be true as shown by the data for the acid
hydrolysis of chloride complexes in which various pyridin
are present

[Co(en)2(X-py)Cl]+2 + H2O [Co(en)2(X-py)H2O]+3 + Cl-

It is found that increasing the basicity of pyridin does

indeed increasing the rate of reaction

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Cis effect in octahedral complexes

• Certain ligands such as the thiocyanate

and hydroxide ions greatly accelerate the
hydrolysis of complex when cis to the
leaving groups
[Co(en)2(OH) Cl]+n + H2O → [Co(en)2(OH) (H2O)]+n+1

N N

N N N N
M M
N OH N OH
Cl OH2
Cis
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• Ligan yang mempunyai efek cis yang baik
adalah ligan yg punya pasangan e- yang
tidak disumbangkan selain untuk berikatan
sigma
• Pasangan e- didonorkan untuk membentuk
ikatan π antara p-d
• Ligan yg memberi efek cis yg negatif : ligan
yg kurang pasangan sunyi selain utk
berikatan sigma dan ligan aseptor π seperti
nitro
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 N
Overlap of filled p orbital of C with vacant
a) p orbital or b) d2sp3 hybrid orbital of
N Co
cobalt in a 5-coordinated square pyramidal
C activated complex resulting from the
a) dissociation of L from cis-[CoN4CL]. The
two N ligands not shown
N

N
N Co
c) No overlap of filled p
C orbital of C with vacant
b) d2sp3 hybrid orbital of cobalt C Co
in a 5-coordinated square
pyramidal activated complex
resulting from the dissociation
of X from trans-[CoN4CL]. N c)
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