Reaction Mechanisms ofInorganic and OrganometallicSystems

ROBERT B . JORDAN

1, Tools of the Trade, 1

1 .1 Basic Terminology, 11 .2 Analysis of Rate Data, 21 .3 Concentration Variables and First-Order Rates, 91 .4 Complex Rate Laws, 1 01 .5 Complex Kinetic Systems, 1 11 .6 Temperature Dependence of Rate Constants, 1 31 .7 Pressure Dependence of Rate Constants, 1 61 .8 Ionic Strength Dependence of Rate Constants, 1 71 .9 Diffusion-Controlled Rate Constants, 1 9

Rate Law and Mechanism, 23

2.1 Steady-State Approximation, 2 32.2 Rapid Equilibrium Assumption, 2 52.3 Principle of Detailed Balancing, 272.4 Principle of Microscopic Reversibility, 27

3 Ligand Substitution Reactions, 2 9

3.1 Operational Approach to Classification of Substitution Mechanisms, 29

3.2 Operational Tests for the Stoichiometric Mechanism, 3 03.3 Examples of Tests for a Dissociative Mechanism, 3 63.4 Operational Test of an Associative Mechanism, 403.5 Operational Tests for the Intimate Mechanism, 4 33.6 Some Special Effects, 573.7 Variation of Substitution Rates with Metal Ion, 6 53.8 Ligand Substitution on Labile Transition-Metal Ions, 7 4

3 .9 Kinetics of Chelate Formation, 8 1

4 Stereochemical Change, 91

4.1 Types of Ligand Rearrangements, 9 14 .2 Optical and Geometrical Isomer Interconversion, 944.3 Stereochemical Change in Five-Coordinate Systems, 1024.4 Fluxional Organometallic Compounds, 103

5 Reaction Mechanisms of Organometallic Systems, 11 95.1 Ligand Substitution Reactions, 1195.2 Insertion Reactions, 13 05 .3 Oxidative Addition Reactions, 13 65 .4 Reactions of Alkenes, 1425 .5 Catalytic Hydrogenation of Alkenes, 1465 .6 Homogeneous Catalysis by Organometallic Compounds, 15 9

6 Oxidation-Reduction Reactions, 16 76.1 Classification of Reactions, 1676.2 Outer-Sphere Electron-Transfer Theory, 1706.3 Differentiation of Inner-Sphere and Outer-Sphere Mechanisms, 18 36.4 Bridging Ligand Effects in Inner-Sphere Reactions, 1846.5 Intervalence Electron Transfer, 19 06.6 Electron Transfer in Metalloproteins, 194

7 Inorganic Photochemistry, 1987.1 Basic Terminology, 19 87.2 Kinetic Factors Affecting Quantum Yields, 20 07 .3 Photochemistry of Cobalt(III) Complexes, 20 17 .4 Photochemistry of Rhodium(III) Complexes, 2057.5 Photochemistry of Chromium(III) Complexes, 20 77.6 Ru(II) Polypyridine Complexes, 21 17 .7 Organometallic Photochemistry, 21 17 .8 Photochemical Generation of Reaction Intermediates, 219

8 Bioinorganic Systems, 2248.1 Vitamin B 12 , 2248 .2 A Zinc(fI) Enzyme: Carbonic Anhydrase, 23 38.3 Enzymic Reactions of Dioxygen, 239

Problems, 255

Chemical Abbreviations, 26 7

Index, 269