Reddy K Veera - Reaction Mechanisms in Metal Complexes

NEW AGE REFERENCE
REACTION
MECHANISMS IN
METAL COMPLEXES
K VEERA REDDY
NEW AGE INTERNATIONAL PUBLISHERS

REACTION MECHANISMS IN
METAL COMPLEXES
K VEERA REDDY
PhD
Professor of Chemistry (Retd.)
Osmania University, Hyderabad, Telangana
ISBN : 978 93 89802 15 3

Price : 999.00
Pub Date : 2021
Format : Hardbound
Extent : 240 Pages
About the Book: Contents:
Most of the modern textbooks of inorganic chemistry invariably devote a chapter on ‘Inorganic Reaction • Reaction Parameters
Mechanisms’ with the depth of the coverage being quite variable and compact. In this context this book serves two-
• Kinetic Aspects of Metal
fold need. It is primarily designed to help the students preparing for the semester courses at PG Level of many Complexes
national and international universities. Secondly, the teachers who have been sailing through the topics incorporated
• Substitution Reactions:
in the book might thoroughly enjoy the classroom-friendly narration of the subject. The contents of the book are
Octahedral Metal
organized in a style and content that suits the curricula of several Indian universities offering this subject. Complexes
About the Author: • Substitution Reactions:
Dr. K Veera Reddy retired as a Professor and Head, Department of Chemistry from Osmania University, Hyderabad. He Square Planar Metal
has also served as the Principal, University College of Science from 2005-2009 and Vice-Chancellor of Satavahana Complexes
University, Telangana from 2012-2015. After receiving his M.Sc. (1974) and Ph.D. (1980) degrees from Osmania • Electron-Transfer
University, he served as the faculty of the university continuously as an Assistant Professor (1980), an Associate Professor Reactions
(1984) and Professor (1992) till his superannuation in June 2011. During his stint in teaching he visited United States for a • Reaction Pathways in
post-doctoral stint (1988-90) and worked as a Research Associate at the Department of Chemistry, Case Western Reserve Organometallic
University, Cleveland, Ohio. He has a vast teaching experience of over 31 years and has the unique distinction of Complexes
delivering over 1000 lectures as a Resource Person at several Workshops, Refresher Courses and Orientation Programmes • Stereochemical
organized by many colleges, universities and research centers, particularly on the topics related to ‘Symmetry, Group Rearrangements
Theory and Spectroscopy’. He was a visiting professor to some universities. He is recipient of coveted ‘Best Teacher • Reactions in Bological
Award’ for the year 2007. He served as the First and Founder Director of University Foreign Relations Office (UFRO, Systems
1999–2004), an exclusive single-window International Office of Osmania University.
His main research interests are in Bio-coordination Chemistry, particularly modeling of enzymes such as
carboxypeptidase-A (CPA) and peptidyl-α-amidating monooxygenase (PMA). Design, synthesis and
characterization of poly functional ligands of biological significance and their platinum group metal complexes as
anti-cancer drugs have also been the other major areas of his research. He was the recipient of major research grants
from DST. He has published 25 research articles in national and international journals and has so far authored six
books.
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9999709935 93159052989315905295
REACTION
MECHANISMS IN
METAL COMPLEXES
K VEERA REDDY
PhD
Professor of Chemistry (Retd.)
Osmania University
Hyderabad, Telangana
NEW AGE
REFERENCE
NEW AGE INTERNATIONAL (P) LIMITED, PUBLISHERS

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Preface
The book is designed to fit into the needs of teachers, post-graduate students
and research scholars working in the area of transition metal complexes.
The level of the book is that of an introduction to the most important and
interesting concepts underlying the reaction chemistry, particularly that of
metal complexes.
My goal in writing this book has been to cover only those topics that are
related to the singular concept of the role of metal ions in mechanisms of
such reactions spanning from simple metal complexes to those in biological
systems. This book, in comparison with the other existing good books
in the field, has longer and more lucid explanation of difficult concepts,
more teacher and student-friendly illustrations with suitable examples of
reactions. Transitions between the paragraphs in a given chapter and from
chapter to chapter are made smooth with no long jumps. This sequencing
was adhered to since any branch of Chemistry is a subject that builds on
the previous knowledge. Also, there is more repetition of important points.
I believe the contents of the book are presented in less terse, more readable
and easier-to-learn fashion. The style and pedagogical pattern of the book
has emerged from the lectures of the author for a two-semester course at
post-graduate level of Osmania University for nearly 20 years.
The book begins with the description on the tools of the trade in
Chapter 1 and sails gradually and smoothly through the main body of
the subject of the reaction mechanisms in metal complexes in subsequent
chapters. Chapter 2, while emphasizing on the kinetic aspects of metal
complexes, also brings out some possible correlations between the
thermodynamic and kinetic characteristics of the reacting metal complex.
Since the major type of reactions undergone by metal complexes are
substitution type, Chapters 3 and 4 deal with these areas of importance
vii

viii Reaction Mechanisms in Metal Complexes
with reference to two important stereochemical geometries of metal

complexes, octahedral and square planar, respectively. With the award
of 1983 Nobel Prize to Professor Henry Taube for his work on ‘electron-
transfer reactions’, the contents of Chapter 5 on ‘Electron-Transfer Reactions
in Metal Complexes’ assume significance. For his pioneering work in
this area and invaluable contributions that literally built the subject of
‘Inorganic Reaction Mechanisms’ parallel to that in organic reactions, Prof.
Taube deservingly fits into the sobriquet of ‘Father of Inorganic Reaction
Mechanisms’.
Chapter 6 is the best meeting ground for organic and inorganic
chemists. There is an interplay of several principles involved in the
reactions belonging to organic and inorganic chemistry. The contents
presented in this chapter encompass several fundamental processes that
are aided by the metal ions for faster, efficient and selective product
yielding reactions. A near exclusive analysis of certain spontaneous
molecular rearrangements and its dynamics is presented in Chapter 7. Each
of the sections presented in Chapter 8 begins with a brief description on
the structure of a biomolecule and proceeds gradually through some basic
concepts concerning the utility of metal ions in the reactivity of biological
systems. Certain metal ions are essential to the living cells, although H,
C, N, O, S and P are the basic elements used for constructing the building
blocks of biological compounds. The coordinate nature of interactions of
these metal ions with biological molecules and their role in conducting the
corresponding vital processes has been discussed with a suitable interface
of organic and inorganic principles.
Some useful ‘Study Questions’ are provided at the end of the book and
working through them is the only way to master the theme of the book.
This exercise you may take it as an additional drill for gaining the skills of
the subject of this kind that has subtle character. No book is complete by
itself and the frontiers of knowledge have no boundaries.
I sincerely thank the many people, particularly my classroom students,
whose help and suggestions were so valuable in the creation of this
book. I would be glad to welcome all the readers, students and teachers,
to scrupulously and sincerely browse through all the pages, and offer
suggestions to help improve any of the aspects of the text presented in the
book. My special thanks are due to the Management and all those people
at the New Age Publications (P) Ltd., who have assisted me in bringing
out this book in the present beautiful form.
Hyderabad 500 007 K. Veera Reddy

Contents
Preface vii
1. Reaction Parameters 1–9

1.1 Reaction Parameters 1
1.2 Mechanism of the Reaction 6
1.3 Energy Profile of a Reaction 7
2. Kinetic Aspects of Metal Complexes 10–18

2.1 Labile and Inert Complexes 10
2.2 Thermodynamic Stability 12
2.3 Kinetic Application of Valence Bond Theory 13
2.4 Kinetic Application of Crystal Field Theory 14
3. Substitution Reactions: Octahedral Metal Complexes 19–46

3.1 Types of Reactions in Metal Complexes 19
3.2 Substitution Reactions 19
3.3 Substitution Reactions in Octahedral Complexes 20
3.4 Octahedral Complexes as Ideal Systems for Kinetic Investigations 26
3.5 Acid Hydrolysis 27
3.6 Base Hydrolysis 36
3.7 Anation Reactions 40
3.8 Reactions Without Metal-Ligand Bond Cleavage 41
4. Substitution Reactions: Square Planar Metal Complexes 47–64

4.1 Metal Ions Favouring Square Planar Geometry 47
4.2 The Trans-Effect 48
4.3 Applications of Trans-Effect 52
4.4 Theories of Trans-Effect 55
4.5 Mechanism of Substitution Reactions in Square Planar Complexes 58
5. Electron-Transfer Reactions 65–80

5.1 Types of Redox Reactions 65
5.2 Electron-transfer Reactions 66
ix

x Reaction Mechanisms in Metal Complexes
5.3 Outer-sphere Mechanism 66

5.4 Marcus–Hush Theory 70
5.5 Inner-sphere Mechanism 72
5.6 Nature of the Bridging Ligand 75
5.7 Distinguishing between the Inner and Outer-Sphere Mechanism Types 78
5.8 Complementary and Non-complementary Redox Reactions 79
6. Reaction Pathways in Organometallic Complexes 81–128

6.1 Mechanistic Classification of Organometallic Reactions 81
6.2 Isomerization Reactions 82
6.3 Oxidative Addition Reactions 83
6.4 Reductive Elimination Reactions 91
6.5 Insertion Reactions 93
6.6 Reactions of Alkenes 100
6.7 Reactions of Carbon Monoxide 125
7. Stereochemical Rearrangements 129–154

7.1 Rearrangements on Coordinated Ligands 129
7.2 Stereochemical Changes in Octahedral Chelates 131
7.3 Stereochemical Rearrangements in Five-coordinate Complexes 137
7.4 Stereochemical Rearrangements in Four-coordinate Complexes 140
7.5 Fluxionality in Organometallic Systems 142
8. Reactions in Biological Systems 155–210

8.1 Metal Ions Biological Systems 155
8.2 Iron–Sulfur Proteins 156
8.3 Cytochromes 171
8.4 Zinc Enzymes 174
8.5 Vitamin B12 Coenzyme 195
8.6 Enzymic Reactions of Dioxygen 204
8.7 Enzymic Reactions of Nitric Oxide 209
Study Questions 211–219
References 220–224
Appendix I: Nucleophilic Substitution 225–227
Appendix II: Enantiotopic Faces 228–229
Appendix III: Enzymes Versus Metal Complex Catalysts 230

1 Reaction Parameters
The chapter deals with the fundamental aspects related to the reaction
mechanisms and thus providing a basis for understanding the inorganic
reaction mechanisms. The field of inorganic reaction mechanisms lagged
behind an analogous field of organic reaction mechanisms for some time
for various experimental reasons. But later it started developing faster
due to the efforts of Henry Taube (who was awarded the 1983 Nobel
Prize for his work on electron-transfer reactions) and several other
contemporary chemists.
1.1 REACTION PARAMETERS

This preliminary section deals with, in some detail, some of the commonly
encountered kinetic parameters. These parameters are to be evaluated
after performing the experiment for the purpose of finally arriving at a
mechanism in its final and micro details.
1. Rate of a reaction
2. Half-life of a Reaction
3. Catalyst
4. Rate Law
5. Mechanism of a Reaction
6. Energy Profile of a Reaction
(i) Activated Complex
(ii) Transition State
(iii) Intermediate
1.1.1 Rate of Reaction

The rate of a reaction can be defined as the change in concentration of
1
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2 Reaction Mechanisms in Metal Complexes
any of the reactants or products per unit of time. It is a measure of the

speed of the reaction. Some reactions occur so quickly that they appear
to take no time at all. Such reactions are not instantaneous, but they are
extremely fast. The precipitations of insoluble salts belong to this category
of reactions. For example, formation of silver chloride is one such reaction:
Ag+(aq) + Cl–(aq) AgCl(s)

Other reactions take place very slowly and it is often difficult to detect
that reaction is taking place. Rusting of iron is an example of a chemical
reaction between iron, water and oxygen which takes place slowly to give
orange/brown hydrated iron oxides called rust.
Rate Curves: A graph of concentration against time is known as rate
curve. The rate of a reaction can then be given by:
Rate of a reaction = (change in concentration) / (time taken for change)
The kinetic data are usually presented graphically by plotting either,
(i) a reactant concentration against time, or
(ii) a product concentration against time
This is illustrated in Figure 1.1 for the acid hydrolysis of Co(III)
complex. These graphs are called as rate curves.
The rate of a reaction can be expressed conveniently in terms at least two
kinetic parameters:
(i) Rate constant (k) and/or
(ii) Half-life (t½)
The larger the value of the rate constant (k), faster will be the rate of a
reaction. On the other hand, the smaller the value of half-life parameter,
faster will be the rate of a reaction.
1.1.2 Half-life of a Reaction (t½)

t½ is a convenient and quantitative way of expressing the rate of a reaction.
It is the time taken for one-half of the reactants to be converted to products.
For a first order reaction, it is a constant at a particular temperature. It can
also be obtained from the rate constant, using the relationship:
t = 0.693/k
½
k is the first-order rate constant. For example, consider the standard acid
hydrolysis reaction of a Co(III) complex, where it is shown that reaction
can be monitored by either measuring the rate of formation of the product
aquo-complex or the rate of disappearance of the initial reactant chloro-

Reaction Parameters 3
complex. Half-life of the reaction can sometimes be directly read off from
these reaction plots as shown in the Figure 1.1.
acid hydrolysis
[Co(NH3)5Cl]2+ + H2O [Co(NH3)5(H2O)]3+ + Cl–
at 25°C
3+
[Co(NH3)5(H2O)]
t1/2
Conc.
2+
[Co(NH3)5(Cl)]
113 hrs.
Time in hours
Figure 1.1: Acid hydrolysis reaction of a Co(III) complex
1.1.3 Catalyst
Catalysts are chemical substances which increase the rate of a chemical
reaction. They provide an alternative pathway of lower activation energy
than in the absence of a catalyst (see section 1.3.3 and Figure 1.5). The
reaction proceeds via an intermediate substance (which is not usually
isolated) formed between one or more of the reactants and the catalyst.
A catalyst thus can be defined as a substance that speeds up the rate of
reaction without itself undergoing any change. A catalyst has no effect
on the position of a chemical equilibrium or the equilibrium constant. It
however ensures that the position of equilibrium is reached more quickly.
In addition to the catalyst with the above-mentioned characteristics,
there are also substances, which act as inhibitors, promoters and catalyst
poisons.
Inhibitor: A substance that slows down or stops a reaction (even though
present in small amounts) is called an inhibitor. Inhibitors are sometimes
called as negative catalysts since they slow down chemical reactions. They
are believed to operate by reacting with some of the intermediates of the
reaction, thereby reducing the formation of the products.
Promoters: Promoters are substances, which may improve the
performance of a catalyst. They do not alter the rates of reaction when
used alone but support the activity of catalysts.

Catalyst poisons: Catalyst poisons are substances that reduce or

diminish the activity of catalysts. Catalyst poisons such as H2S, Hg(II)
salts, As, CO and HCN greatly reduce the effectiveness of the catalysts. The
effectiveness of the catalyst poisons is thought to be due to their capacity
to bind to the catalytic site of the catalyst. In biological systems, they bind
to proteins, particularly the active sites of enzymes, thus preventing their
normal activity.
1.1.4 Rate Law

The relationship between concentrations of reactants and the rate of reaction
depends on a reaction under investigation. It can only be established by
the experiment. It cannot be determined from the inspection of a balanced
equation for the reaction. Consider the following reactions of common
occurrence:
A
→ Products
A
→ A’ (isomerization)
A
→ B + C (Dissociation)
All these reactions can have simple or complicated mechanisms. Now
consider types of mechanisms in terms of their rate laws.
(i) Simple Mechanism
Consider the reaction,
A
→ Products
Rate ∝ [A]
Rate = k[A]
k is a rate constant, which is a number characteristic of the reaction
rate. k is large for rapid reactions and small for slow reactions.
(ii) Complicated Mechanism
Consider the reaction,
A
→ A´ (in two-steps)
For example,
A + D → E (slow, r. d. s.) …(a)
E + D → A’ + D (fast) …(b)
Rate of formation of E can be written as
E
∝ [A][D], or
= k[A][D] (second-order)

D is acting in this reaction as a catalyst.

Also, if
A + 2B → Products
Rate = k[A][B]2
The reaction is third order, first order in [A] and second order in [B].
1.1.5 Order of a Reaction

Study of the dependence of reaction rate on the concentration of each
reactant enables us to predict about the rate of a reaction. The rate law
or rate equation for a process is a convenient way of communicating the
results of kinetic experiments. To describe the effect of the concentration
of a reactant we need to use the term order. The order of a reaction with a
particular reactant is the power to which the concentration of that reactant
is raised in the rate equation or rate law. Thus, the order of a reaction
depends on the number of species and number of times each species
occurs in the rate law.
Often the order of a reaction is equal to the number of particles present
in the rate-determining step (r. d. s.) of the reaction. However, there are
examples where the order of the reaction is less than the number of
particles in r. d. s. (leading to fractional or zero-order) and the rate law has
nothing to do with the stoichiometry of the reaction.
The most common values for the order of a reaction with respect to a
particular reactant are 0, 1 or 2. Figure 1.2 presents the rate curves for zero,
first and second order reactions:
Zero order
First order
Concentration Seconds order

of reactant
Time
Figure 1.2: Rate curves for zero, first and second order reactions

On the other hand, Figure 1.3 illustrates the variation of reaction rates
with concentration for zero, first and second order reactions:
Second order First order
Reaction
rate Zero order
Concentration
Figure 1.3: Variation of reaction rates with concentration for zero, first and second
order reactions
1.1.6 Molecularity of a Reaction

The molecularity of a reaction is defined as the number of species (atoms,
molecules, radicals or ions) involved in the rate-determining step. The
molecularity of a reaction cannot be found experimentally.
1.2 MECHANISM OF THE REACTION

Historical: Historical evolution of the chemical reactions was very slow.
Until a few decades ago many chemists considered the ‘mechanism’ of a
reaction as a kind of ‘chemical mythology’. And then the explosion came
with an apparent interest in every chemical reaction with respect to the
following:
(i) ‘How’ the charges (electrons) are transferred?
(ii) ‘How’ chemical bonds break and form?
(iii) ‘How’ and ‘what’ intermediates are formed?
A Chemical reaction today: ‘One’ chemical reaction is not ‘one’
reaction any more! It is a series of reactions fast and slow, all occurring in a
sequence of steps, i.e., pathway. The rate of a chemical reaction is dependent
on the nature of this pathway by which the reactants are transformed
into products. This path is called the ‘mechanism’ of the reaction. The
mechanism will give an idea about what, how and how fast it happens in

a chemical reaction. In summary, the mechanism is a detailed, step-by-step

description of a chemical reaction. It is only a hypothesis; it is advanced to
account for the facts.
1.3 ENERGY PROFILE OF A REACTION
1.3.1 Activated Complex

The ‘activated complex’ occupies an energy level called ‘transition state’ which
occurs at the point of highest energy (Figure 1.4). ‘Intermediate’ should not
be confused with ‘activated complex’.
Transition state (1)
Activated complex
Transition state (2)
Intermediate
Activation energy (Ea)

Free
energy
(G)
Reactants
Reaction energy (∆H)
Products
Reaction Coordinate
Figure 1.4: Energy profiles of a reaction
1.3.2 Intermediates
Intermediates are transient chemical species with short-lived existence and
may occur in most reaction sequences. They may exist for long enough to
be detected, isolated and structurally characterized at times. They possess
definite chemical properties and molecular configuration. Though they
are too reactive to be isolated and analyzed; yet there are some physical
methods that could be used to demonstrate their presence. Intermediates
sometimes could be trapped in experiments by adding some substances

that do not react either with the reactants or products but react only with
the intermediates. An adduct of the added substance and the intermediate
could be isolated. The presence of intermediates could be denoted by the
minima in the energy profiles of a reaction (Figure 1.4). Kinetic studies
provide information on the formation of intermediates. For example,
induction periods are caused by the slow and gradual build-up of
intermediates.
1.3.3 Transition States

Transition state is the highest energy level in the energy profile of a reaction.
It should never be confused with the intermediates or activated complexes,
which in fact are material/molecular species. Transition states are denoted
by the maxima in the energy profiles of a reaction. Activated complex is
some hypothetical species that has no definite molecular structure where
some bonds are in the process of breaking and the others in the making. It
is a loose molecular arrangement resembling an adduct formed out of all
the reactants participating in the reaction.
When the reactions are catalyzed, the energy profile will have the
appearance shown in Figure 1.5. This reflects in the fact that a catalyst
simply provides an alternate but lower energy route for a chemical reaction.
The activation energy is lowered in catalyzed reactions as reflected in the
lowered transition state (Figure 1.5).
Transition state
for normal reactions
Activated complex
Transition state
for catalyzed reactions
Free
energy
(G)
Reactants
Reaction Energy (∆H)
Products
Reaction coordinate
Figure 1.5: Energy profiles of a catalyzed and uncatalyzed reaction

The rates of reaction are generally affected by:

(i) Temperature
(ii) Concentration of the reactants
(iii) Effect of Catalyst
(iv) Effect of molecular complexity

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PU
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9999709935 93159052989315905295
REACTION MECHANISMS IN METAL COMPLEXES
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Compliments from to all Faculty Members

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with reference to two important stereochemical geometries of metal

Hyderabad 500 007 K. Veera Reddy

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1. Reaction Parameters 1–9

2. Kinetic Aspects of Metal Complexes 10–18

3. Substitution Reactions: Octahedral Metal Complexes 19–46

4. Substitution Reactions: Square Planar Metal Complexes 47–64

5. Electron-Transfer Reactions 65–80

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5.3 Outer-sphere Mechanism 66

6. Reaction Pathways in Organometallic Complexes 81–128

7. Stereochemical Rearrangements 129–154

8. Reactions in Biological Systems 155–210

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1.1 REACTION PARAMETERS

1.1.1 Rate of Reaction

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any of the reactants or products per unit of time. It is a measure of the

Ag+(aq) + Cl–(aq) AgCl(s)

1.1.2 Half-life of a Reaction (t½)

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Figure 1.1: Acid hydrolysis reaction of a Co(III) complex

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Catalyst poisons: Catalyst poisons are substances that reduce or

1.1.4 Rate Law

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D is acting in this reaction as a catalyst.

1.1.5 Order of a Reaction

Concentration Seconds order

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Second order First order

1.1.6 Molecularity of a Reaction

1.2 MECHANISM OF THE REACTION

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a chemical reaction. In summary, the mechanism is a detailed, step-by-step

1.3 ENERGY PROFILE OF A REACTION

1.3.1 Activated Complex

Transition state (1)

Transition state (2)