Table Of ContentReaction Mechanisms of
Inorganic and Organometallic
Systems
TOPICS IN INORGANIC CHEMISTRY
A Series of Advanced Textbooks in Inorganic Chemistry
Series Editor
Peter C. Ford, University of California, Santa Barbara
Chemical Bonding in Solids, J. Burdett
Reaction Mechanisms of Inorganic and Organometallic Systems,
3rd Edition, R. Jordan
Reaction Mechanisms of
Inorganic and Organometallic
Systems
Third Edition
Robert B. Jordan
OXFORD
UNIVERSITY PRESS
2007
OXPORD
UNIVERSITY PRESS
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Library of Congress Cataloging-in-Publication Data
Jordan, Robert B.
Reaction mechanisms of inorganic and organometallic systems / Robert
B. Jordan.—3rd ed
p. cm.
Includes bibliographical references and index.
ISBN 978-0-19-530100-7
1. Reaction mechanisms (Chemistry) 2. Organometallic compounds. 3. Inorganic
compounds. I. Title.
QD502J67 2006
41'.39—dc25 2006052498
987654321
Printed in the United States of America
on acid-free paper
Preface
This book evolved from the lecture notes of the author for a one-
semester course given to senior undergraduates and graduate students
over the past 20 years. This third edition presents an updating of the
material to cover the literature through to the end of 2005, with
occasional excursions to early 2006. As a result, the total number of
references has increased from about 660 in the second edition to over
1570 in the present one, and 140 pages of text have been added; this
seems to be a clear testament to the vitality of the subject area. A new
Chapter 9 on kinetics in heterogeneous systems has been added. This
area has long been the domain of chemical engineers, but it is of
increasing relevance to inorganic kineticists who are studying catalytic
processes, such as hydrogenation and carbonylation reactions, where
gas/liquid mass transfer is involved. This chapter also covers the kinetic
aspects of adsorption and reaction of species on solids, and the question
of whether the reaction is really homogeneous or heterogeneous.
The overall organization of the first edition has been retained. The
first two chapters cover basic kinetic and mechanistic terminology and
methodology. This material includes new sections on the analysis of
data under second-order conditions, Curtin-Hammett conditions and an
expanded discussion of pressure effects. New material has been added at
various points throughout Chapters 3 and 4. The coverage of
organometallic systems in Chapter 5 has been increased substantially,
primarily with material on metal hydrides, catalytic hydrogenation and
asymmetric hydrogenation. The inverted region and activation
parameters for electron-transfer reactions predicted by Marcus theory
have been added to Chapter 6, along with an expanded discussion of
intervalence electron transfer. The recently revised assignment of the
electronic spectra of metal carbonyls has resulted in substantial revisions
to photochemical interpretations in Chapter 7. The coverage of selected
bioinorganic systems in Chapter 8 has been extended to include
methylcobalamin as a methyl transferase and the chemistry of nitric
oxide synthase. Chapter 10 on experimental methods and their
applications is largely unchanged. Some new problems for each chapter
have been added.
There is more material than can be covered in depth in one semester,
but the organization allows the lecturer to omit or give less coverage to
certain areas without jeopardizing an understanding of other areas. It is
assumed that the students are familiar with elementary crystal field
v
vi Preface
theory and its applications to electronic spectroscopy and energetics,
and concepts of organometallic chemistry, such as the 18-electron rule,
71 bonding and coordinative unsaturation. For the material in the first
two chapters, some background from a physical chemistry course would
be useful, and familiarity with simple differential and integral calculus is
assumed.
It is expected that students will consult the original literature to obtain
further information and to gain a feeling for the excitement in the field.
This experience also should enhance their ability to critically evaluate
such work. Many of the problems at the end of the book are taken from
the literature, and original references are given; outlines of answers to
the problems will be supplied to instructors who request them from the
author.
The issue of units continues to be a vexing one in this area. A major
goal of this course has been to provide students with sufficient
background so that they can read and analyze current research papers.
To do this and be able to compare results, the reader must be vigilant
about the units used by different authors. Energy units are a special
problem, since both joules and calories are in common usage. Both
units have been retained in the text, with the choice made on the basis of
the units in the original work as much as possible. However, within
individual sections the text uses one energy unit. Bond lengths are given
in angstroms, which are still commonly quoted for crystal structures.
The formulas for various calculations are given in the original or most
common format, and units for the various quantities are always
specified.
The author is greatly indebted to all of those whose research efforts
have provided the core of the material for this book. The author is
pleased to acknowledge those who have provided the inspiration for this
book: first, my parents, who contributed the early atmosphere and
encouragement; second, Henry Taube, whose intellectual stimulation
and experimental guidance ensured my continuing enthusiasm for
mechanistic studies. I am only sorry that I did not finish this edition
soon enough for Henry to see that I did make the changes he suggested.
Finally and foremost, Anna has been a vital force in the creation of this
book through her understanding of the time commitment, her
comments, criticisms and invaluable editorial assistance in producing the
camera-ready manuscript. However, the inevitable remaining errors and
oversights are entirely the responsibility of the author.
R.B.J.
Edmonton, Alberta
June 2006
Contents
1 Tools of the Trade, 1
1.1 Basic Terminology, 1
1.2 Analysis of Rate Data, 3
1.3 Concentration Variables and Rate Constants, 12
1.4 Complex Rate Laws, 15
1.5 Complex Kinetic Systems, 15
1.6 Temperature Dependence of Rate Constants, 17
1.7 Pressure Dependence of Rate Constants, 21
1.8 Ionic Strength Dependence of Rate Constants, 24
1.9 Diffusion-Controlled Rate Constants, 25
1.10 Molecular Modeling and Theory, 28
2 Rate Law and Mechanism, 31
2.1 Qualitative Guidelines, 31
2.2 Steady-State Approximation, 32
2.3 Rapid-Equilibrium Assumption, 34
2.4 Curtin-Hammett Conditions, 36
2.5 Rapid-Equilibrium or Steady-State?, 37
2.6 Numerical Integration Methods, 3 8
2.7 Principle of Detailed Balancing, 39
2.8 Principle of Microscopic Reversibility, 40
3 Ligand Substitution Reactions, 43
3.1 Operational Approach to Classification of Substitution Mechanisms, 43
3.2 Operational Tests for the Stoichiometric Mechanism, 44
3.3 Examples of Tests for a Dissociative Mechanism, 49
3.4 Operational Test for an Associative Mechanism, 54
3.5 Operational Tests for the Intimate Mechanism, 57
3.6 Some Special Effects, 73
3.7 Variation of Substitution Rates with Metal Ion, 83
3.8 Ligand Substitution on Labile Transition-Metal Ions, 94
3.9 Kinetics of Chelate Formation, 100
4 Stereochemical Change, 114
4.1 Types of Ligand Rearrangements, 114
4.2 Geometrical and Optical Isomerism in Octahedral Systems, 119
4.3 Stereochemical Change in Five-Coordinate Systems, 128
4.4 Isomerism in Square-Planar Systems, 130
4.5 Fluxional Organometallic Compounds, 130
5 Reaction Mechanisms of Organometallic Systems, 150
5.1 Ligand Substitution Reactions, 150
5.2 Insertion Reactions, 168
5.3 Oxidative Addition Reactions, 177
vii
viii Contents
5.4 Reductive Elimination Reactions, 188
5.5 Reactions of Alkenes, 188
5.6 Catalytic Hydrogenation of Alkenes, 195
5.7 Homogeneous Catalysis by Organometallic Compounds, 225
6 Oxidation-Reduction Reactions, 253
6.1 Classification of Reactions, 253
6.2 Outer-Sphere Electron-Transfer Theory, 256
6.3 Differentiation of Inner-Sphere and Outer-Sphere Mechanisms, 273
6.4 Bridging Ligand Effects in Inner-Sphere Reactions, 274
6.5 Intervalence Electron Transfer, 281
6.6 Electron Transfer in Metalloproteins, 285
7 Inorganic Photochemistry, 292
7.1 Basic Terminology, 292
7.2 Kinetic Factors Affecting Quantum Yields, 294
7.3 Photochemistry of Cobalt(III) Complexes, 295
7.4 Photochemistry of Rhodium(III) Complexes, 301
7.5 Photochemistry of Chromium(III) Complexes, 304
7.6 Photochemistry of Ruthenium(II) Complexes, 310
7.7 Organometallic Photochemistry, 313
7.8 Photochemical Generation of Reaction Intermediates, 327
8 Bioinorganic Systems, 337
8.1. Basic Terminology, 337
8.2 Terms and Methods of Enzyme Kinetics, 338
8.3 Vitamin B , 341
12
8.4 A Zinc(II) Enzyme: Carbonic Anhydrase, 356
8.5 Enzymic Reactions of Dioxygen, 361
8.6 Enzymic Reactions of Nitric Oxide, 373
9 Kinetics in Heterogeneous Systems, 391
9.1 Gas/Liquid Heterogeneous Systems, 391
9.2 Gas/Liquid/Solid Heterogeneous Systems, 400
9.3 Where is the Catalyst?, 409
10 Experimental Methods, 422
10.1 Flow Methods, 423
10.2 Relaxation Methods, 428
10.3 Electrochemical Methods, 431
10.4 Nuclear Magnetic Resonance Methods, 435
10.5 Electron Paramagnetic Resonance Methods, 446
10.6 Pulse Radiolysis Methods, 448
10.7 Flash Photolysis Methods, 451
Problems, 457
Chemical Abbreviations, 488
Index, 491
Reaction Mechanisms of
Inorganic and Organometallic
Systems
