Homogeneous Catalysis with Metal Complexes: Kinetic Aspects and Mechanisms
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Homogeneous Catalysis with Metal Complexes: Kinetic Aspects and Mechanisms

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Oleg N. Temkin
1565 g
254x198x43 mm

Notations and Abbreviations xi

Preface to English Edition xvii

Preface xix

Acknowledgments xxi

About the Author xxiii

Introduction 1

1 State-of-the-Art in the Theory of Kinetics of Complex Reactions 21

1.1 Main concepts of the Horiuti-Temkin theory of steady-state reactions 21

1.1.1 Reaction mechanism: Stoichiometry and routes 22

1.1.2 Kinetics: Reaction rates with respect to substances and over routes 32

1.1.3 Kinetic polynomial 42

1.1.4 Determining the number of independent parameters in a kinetic model. The problem of identifiability of parameters 44

1.2 Quasi-steady-state and quasi-equilibrium approximations in chemical kinetics 47

1.2.1 Theoretical criteria of quasi-steady-state intermediate concentrations and quasi-equilibrium steps 49

1.2.2 Experimental criteria of applicability of quasi-steady-state approximation in various systems 60

1.3 Methods of graph theory in chemical kinetics and in theory of complex reaction mechanisms 62

1.3.1 Linear mechanisms 62

1.3.2 Nonlinear mechanisms 71

1.3.3 Other fields of application of kinetic and bipartite graphs in chemical kinetics and in theory of complex reaction mechanisms 76

1.4 Elementary steps - Selection rules 79

1.4.1 Main postulates, laws, and principles 79

1.4.2 Energy selection rules for elementary steps 88

1.4.3 Quantum-chemical selection rules for elementary steps 92

1.4.4 Topological selection rules for elementary steps 108

References 113

2 Complexity Functions of Catalysts and Reactants in Reactions Involving Metal Complexes 121

2.1 Mononuclear metal complexes 122

2.1.1 Complexity functions: variants I and II 134

2.1.2 Complexity functions: variants III and IV 149

2.1.3 General problems and recommendations 165

2.2 Polynuclear complexes in homogeneous catalytic and noncatalytic reactions 167

2.2.1 Systems with formation of associates 168

2.2.2 Systems with mononuclear and polynuclear complexes of various types 182

2.3 Catalysis with polynuclear copper(I) halide complexes in superconcentrated solutions 193

2.3.1 Copper(I) chloride complexes in solution and in crystalline state 194

2.3.2 Kinetics of catalytic reactions of alkynes in concentrated NH4Cl-CuCl aqueous solutions at constant complexity functions FCu and FCl 203

2.3.3 Determination of compositions of catalytically active copper(I) complexes in various reactions 210

2.3.4 Studying À and à complexes of copper(I) with alkynes in crystalline state and in solution 216

2.3.5 Mechanisms of acetylene dimerization and hydrocyanation reactions. Crystallochemical aspects 227

References 231

3 Multi-Route Mechanisms in Reactions Involving Metal Complexes 239

3.1 Factors accounting for the appearance and kinetic features of multi-route mechanisms 239

3.2 Analysis of multi-route reaction kinetics 246

3.3 Conjugation nodes and artificial multi-route character 271

3.4 Conjugate processes 304

3.4.1 Classical approach 305

3.4.2 Kinetic and thermodynamic conjugation in consecutive reactions 309

3.4.3 Conjugation in chain reactions 317

3.4.4 Conclusions 323

References 328

4 Polyfunctional Catalytic Systems 335

4.1 Oxidation reactions of organic and inorganic compounds 341

4.1.1 Oxidation of alkenes 341

4.1.2 Oxidation of 1,3-dienes 356

4.1.3 Oxidation of alkynes and arenes 366

4.1.4 Oxidation of inorganic compounds 369

4.2 Reactions of chlorination and oxidative chlorination of organic compounds 372

4.2.1 Oxidative chlorination of alkynes 372

4.2.2 Oxidative chlorination of 1,3-dienes 384

4.2.3 Polyfunctional catalytic systems in chlorination reactions 386

4.3 Oxidative carbonylation of organic compounds 389

4.3.1 Oxidative carbonylation of HY molecules (Y = OR, OPh, NR2, Ar, Alk) 390

4.3.2 Oxidative carbonylation of alkenes, dienes, and alkynes 400

4.4 Additive carbonylation of alkynes, alkenes, dienes, and alcohols 408

4.5 Substitution
This book presents a comprehensive summary of the results obtained over the last sixty years in the field of kinetics and mechanisms of organic and inorganic reactions catalyzed with metal complexes.
The specificity of the catalytic reaction kinetics in the presence of the different form of mono- and polynuclear metal complexes and nanoclusters is discussed. The multiroute mechanisms and the methods of their identification as well as approaches to the polyfunctional catalytic systems kinetics are presented. In addition, the mechanisms of active centers formation and the real, non-ideal catalysts action are systematized and classified. The role and the place of kinetic methods in mechanism studies and the foundation of a rational strategy of theoretically-based kinetic model design is also considered. The kinetic models and mechanisms of many homogeneous catalytic processes employed in synthetic and commercial chemistry are presented.