Homogeneous Catalysis with Metal Complexes -- Contents -- Notations and Abbreviations -- Preface to English Edition -- Preface -- Acknowledgments -- About the Author -- Introduction -- 1 State-of-the-Art in the Theory of Kinetics of Complex Reactions -- 1.1 Main concepts of the Horiuti-Temkin theory of steady-state reactions -- 1.1.1 Reaction mechanism: Stoichiometry and routes -- 1.1.2 Kinetics: Reaction rates with respect to substances and over routes -- 1.1.3 Kinetic polynomial -- 1.1.4 Determining the number of independent parameters in a kinetic model. The problem of identifiability of parameters -- 1.2 Quasi-steady-state and quasi-equilibrium approximations in chemical kinetics -- 1.2.1 Theoretical criteria of quasi-steady-state intermediate concentrations and quasi-equilibrium steps -- 1.2.2 Experimental criteria of applicability of quasi-steady-state approximation in various systems -- 1.3 Methods of graph theory in chemical kinetics and in theory of complex reaction mechanisms -- 1.3.1 Linear mechanisms -- 1.3.2 Nonlinear mechanisms -- 1.3.3 Other fields of application of kinetic and bipartite graphs in chemical kinetics and in theory of complex reaction mechanisms -- 1.4 Elementary steps - Selection rules -- 1.4.1 Main postulates, laws, and principles -- 1.4.2 Energy selection rules for elementary steps -- 1.4.3 Quantum-chemical selection rules for elementary steps -- 1.4.4 Topological selection rules for elementary steps -- References -- 2 Complexity Functions of Catalysts and Reactants in Reactions Involving Metal Complexes -- 2.1 Mononuclear metal complexes -- 2.1.1 Complexity functions: variants I and II -- 2.1.2 Complexity functions: variants III and IV -- 2.1.3 General problems and recommendations -- 2.2 Polynuclear complexes in homogeneous catalytic and noncatalytic reactions -- 2.2.1 Systems with formation of associates.

2.2.2 Systems with mononuclear and polynuclear complexes of various types -- 2.3 Catalysis with polynuclear copper(I) halide complexes in superconcentrated solutions -- 2.3.1 Copper(I) chloride complexes in solution and in crystalline state -- 2.3.2 Kinetics of catalytic reactions of alkynes in concentrated NH4Cl-CuCl aqueous solutions at constant complexity functions FCu and FCl -- 2.3.3 Determination of compositions of catalytically active copper(I) complexes in various reactions -- 2.3.4 Studying π and σ complexes of copper(I) with alkynes in crystalline state and in solution -- 2.3.5 Mechanisms of acetylene dimerization and hydrocyanation reactions. Crystallochemical aspects -- References -- 3 Multi-Route Mechanisms in Reactions Involving Metal Complexes -- 3.1 Factors accounting for the appearance and kinetic features of multi-route mechanisms -- 3.2 Analysis of multi-route reaction kinetics -- 3.3 Conjugation nodes and artificial multi-route character -- 3.4 Conjugate processes -- 3.4.1 Classical approach -- 3.4.2 Kinetic and thermodynamic conjugation in consecutive reactions -- 3.4.3 Conjugation in chain reactions -- 3.4.4 Conclusions -- References -- 4 Polyfunctional Catalytic Systems -- 4.1 Oxidation reactions of organic and inorganic compounds -- 4.1.1 Oxidation of alkenes -- 4.1.2 Oxidation of 1,3-dienes -- 4.1.3 Oxidation of alkynes and arenes -- 4.1.4 Oxidation of inorganic compounds -- 4.2 Reactions of chlorination and oxidative chlorination of organic compounds -- 4.2.1 Oxidative chlorination of alkynes -- 4.2.2 Oxidative chlorination of 1,3-dienes -- 4.2.3 Polyfunctional catalytic systems in chlorination reactions -- 4.3 Oxidative carbonylation of organic compounds -- 4.3.1 Oxidative carbonylation of HY molecules (Y = OR, OPh, NR2, Ar, Alk) -- 4.3.2 Oxidative carbonylation of alkenes, dienes, and alkynes.

4.4 Additive carbonylation of alkynes, alkenes, dienes, and alcohols -- 4.5 Substitution and addition reactions in alkyne chemistry -- 4.6 General problems in PFCS theory and practice -- 4.6.1 PFCSs and principles of their functioning -- 4.6.2 Kinetic and chemical functions of p-benzoquinone and other quinones in PFCSs -- 4.6.3 Variants of association of catalytic reactions and catalytic systems -- References -- 5 Mechanisms of Formation of Catalytically Active Metal Complexes -- 5.1 Main stages of catalytic process -- 5.2 Chemical reactions involved in the formation of active centers -- 5.3 Mechanisms of active center formation in particular processes -- 5.3.1 Mechanisms of active metal complex formation in PdBr2 -LiBr-P(OPh)3-HBr-n-C4H9OH catalytic system for acrylate synthesis -- 5.3.2 Carbene metal complexes in metathesis of olefins and analogous processes -- 5.3.3 Mechanisms of 1-butene isomerization in Ni[P(OEt)3]4-H2SO4 -MeOH system -- 5.3.4 Features of the formation and decay of active centers in acrylic derivatives synthesis by the Reppe Method -- 5.3.5 Protecting active centers by catalytic process from destruction -- 5.3.6 Mechanism of active center formation in Pd(OAc)2 -PPh3 -p-benzoquinone-MeOH catalytic system for alkyne oxidative carbonylation at ≡C-H bond -- 5.3.7 Catalysis with small palladium(I) halide and carbonyl halide clusters -- 5.3.8 Mechanisms of formation of large cluster complexes and microheterogeneous nanoparticles -- 5.3.9 Synthesis and characterization of giant palladium clusters -- 5.3.10 Approaches to identification of the nature of catalytically active species in solutions of metal complexes -- 5.4 Examples of chain mechanisms and chain carriers of various natures -- 5.5 Classification of mechanisms of real catalytic processes -- References.

6 Nonlinear Effects (Critical Phenomena) in Reaction Dynamics in Homogeneous Catalysis with Metal Complexes -- 6.1 Historical notes -- 6.2 Physicochemical factors responsible for the critical phenomena in homogeneous reactions -- 6.2.1 Thermodynamic features of nonequilibrium processes near and far frome quilibrium -- 6.2.2 Dynamic behavior of systems with linear mechanisms in open reactors with complete mixing -- 6.2.3 Nonlinearity of kinetic models -- 6.2.4 Main principles and methods of analysis of the dynamic behavior of nonlinear systems -- 6.3 Analysis of simple nonlinear kinetic models -- 6.4 Mechanisms of oscillatory catalytic reactions -- 6.4.1 Belousov-Zhabotinskii reaction (BZ reaction) -- 6.4.2 Liquid-phase oxidation of organic compounds by oxygen in Co(OAc)2-Br-CH3COOH system -- 6.4.3 Oxidative carbonylation of alkynes in solutions of palladium complexes -- References -- 7 Rational Strategy for Designing Kinetic Models and Studying Complex Reaction Mechanisms -- 7.1 Stages in the development of chemical kinetics and methodological aspects of the strategy of studying complex reaction mechanisms -- 7.2 Alternative strategies for studying complex reaction mechanisms and designing kinetic models -- 7.2.1 Traditional strategy -- 7.2.2 Rational strategy -- 7.3 Hypothesis generation methods and examples -- 7.4 Hypothesis generation programs: Application examples and related problems -- 7.4.1 Combinatorics on kinetic graphs -- 7.4.2 ChemComb (Comb 1) program -- 7.4.3 MECHEM program -- 7.4.4 NetGen program -- 7.4.5 TAMREAC program -- 7.4.6 ChemNet program -- 7.4.7 Large reaction networks and problems in discrimination of hypotheses and construction of compact kinetic models -- References -- 8 Effect of Medium on Reaction Rates in Homogeneous Catalysis with Metal Complexes.

8.1 Effect of electrolytes on the activity coefficients of reaction medium components -- 8.2 Effect of electrolytes on the solubility of nonelectrolytes (gases and organic compounds) -- 8.3 Effect of electrolytes on the rates of elementary reactions between ions and uncharged substrates -- 8.4 Kinetics of catalytic reactions in concentrated aqueous electrolyte (HCl) solutions -- 8.5 Organic solvents in homogeneous catalysis with metal complexes -- 8.5.1 Main physical and chemical properties of solvents -- 8.5.2 Association of solvents and formation of molecular complexes -- 8.5.3 Metal complexes in organic and aqueous-organic solvents -- 8.5.4 Ion association, ion pairs, and specific salt effect in organic solvents -- 8.6 Strong protonic acids in organic solvents and kinetics of catalytic reactions with metal complexes in these media -- 8.6.1 Structure and properties of strong acid solutions in organic solvents -- 8.6.2 Kinetics of catalytic reactions in HCl-NMP, HCl-C2H5OH, and HCl-C2H5OH-CH3CN systems -- 8.7 Ionic liquids in catalytic chemistry -- References -- Conclusion -- Subject Index -- Index of Metals -- Index of Reactions.