Homogeneous Catalysis with Metal Complexes

Professor Oleg Temkin is a well known specialist in the field of Chemical Kinetics, Catalysis with Metal Complexes, Alkynes Chemistry and Mathematical Chemistry. He is a professor of M.V. Lomonosov Moscow State University of Fine Chemical Technologies.Professor Temkin is a co-author of 3 monographs and 2 Chapters in monographs, as well as more than 360 scientific publications including reviews, in such journals as J. Mol. Catal., Organometallics, J. Phys. Chem., J. Chem. Soc. Chem. Commun., Inorg. Chim. Acta,? Langmuir, J. Chem.Ed., React. Kinet. Catal. Lett., J. Chem. Inf. Comput. Sci.,? Mathem.Chem., J. Comput. Chem., J. Mol. Structure(Theochem) as well as in Russian Journals.

• Notations and Abbreviations xi Preface to English Edition xviiPreface xixAcknowledgments xxiAbout the Author xxiiiIntroduction 11 State-of-the-Art in the Theory of Kinetics of Complex Reactions 211.1 Main concepts of the Horiuti–Temkin theory of steady-state reactions 211.1.1 Reaction mechanism: Stoichiometry and routes 221.1.2 Kinetics: Reaction rates with respect to substances and over routes 321.1.3 Kinetic polynomial 421.1.4 Determining the number of independent parameters in a kinetic model. The problem of identifiability of parameters 441.2 Quasi-steady-state and quasi-equilibrium approximations in chemical kinetics 471.2.1 Theoretical criteria of quasi-steady-state intermediate concentrations and quasi-equilibrium steps 491.2.2 Experimental criteria of applicability of quasi-steady-state approximation in various systems 601.3 Methods of graph theory in chemical kinetics and in theory of complex reaction mechanisms 621.3.1 Linear mechanisms 621.3.2 Nonlinear mechanisms 711.3.3 Other fields of application of kinetic and bipartite graphs in chemical kinetics and in theory of complex reaction mechanisms 761.4 Elementary steps – Selection rules 791.4.1 Main postulates, laws, and principles 791.4.2 Energy selection rules for elementary steps 881.4.3 Quantum-chemical selection rules for elementary steps 921.4.4 Topological selection rules for elementary steps 108References 1132 Complexity Functions of Catalysts and Reactants in Reactions Involving Metal Complexes 1212.1 Mononuclear metal complexes 1222.1.1 Complexity functions: variants I and II 1342.1.2 Complexity functions: variants III and IV 1492.1.3 General problems and recommendations 1652.2 Polynuclear complexes in homogeneous catalytic and noncatalytic reactions 1672.2.1 Systems with formation of associates 1682.2.2 Systems with mononuclear and polynuclear complexes of various types 1822.3 Catalysis with polynuclear copper(I) halide complexes in superconcentrated solutions 1932.3.1 Copper(I) chloride complexes in solution and in crystalline state 1942.3.2 Kinetics of catalytic reactions of alkynes in concentrated NH4Cl–CuCl aqueous solutions at constant complexity functions FCu and FCl 2032.3.3 Determination of compositions of catalytically active copper(I) complexes in various reactions 2102.3.4 Studying π and σ complexes of copper(I) with alkynes in crystalline state and in solution 2162.3.5 Mechanisms of acetylene dimerization and hydrocyanation reactions. Crystallochemical aspects 227References 2313 Multi-Route Mechanisms in Reactions Involving Metal Complexes 2393.1 Factors accounting for the appearance and kinetic features of multi-route mechanisms 2393.2 Analysis of multi-route reaction kinetics 2463.3 Conjugation nodes and artificial multi-route character 2713.4 Conjugate processes 3043.4.1 Classical approach 3053.4.2 Kinetic and thermodynamic conjugation in consecutive reactions 3093.4.3 Conjugation in chain reactions 3173.4.4 Conclusions 323References 3284 Polyfunctional Catalytic Systems 3354.1 Oxidation reactions of organic and inorganic compounds 3414.1.1 Oxidation of alkenes 3414.1.2 Oxidation of 1,3-dienes 3564.1.3 Oxidation of alkynes and arenes 3664.1.4 Oxidation of inorganic compounds 3694.2 Reactions of chlorination and oxidative chlorination of organic compounds 3724.2.1 Oxidative chlorination of alkynes 3724.2.2 Oxidative chlorination of 1,3-dienes 3844.2.3 Polyfunctional catalytic systems in chlorination reactions 3864.3 Oxidative carbonylation of organic compounds 3894.3.1 Oxidative carbonylation of HY molecules (Y = OR, OPh, NR2, Ar, Alk) 3904.3.2 Oxidative carbonylation of alkenes, dienes, and alkynes 4004.4 Additive carbonylation of alkynes, alkenes, dienes, and alcohols 4084.5 Substitution and addition reactions in alkyne chemistry 4124.6 General problems in PFCS theory and practice 4234.6.1 PFCSs and principles of their functioning 4234.6.2 Kinetic and chemical functions of p-benzoquinone and other quinones in PFCSs 4264.6.3 Variants of association of catalytic reactions and catalytic systems 436References 4425 Mechanisms of Formation of Catalytically Active Metal Complexes 4535.1 Main stages of catalytic process 4545.2 Chemical reactions involved in the formation of active centers 4575.3 Mechanisms of active center formation in particular processes 4685.3.1 Mechanisms of active metal complex formation in PdBr2 –LiBr–P(OPh)3–HBr–n-C4H9OH catalytic system for acrylate synthesis 4685.3.2 Carbene metal complexes in metathesis of olefins and analogous processes 4715.3.3 Mechanisms of 1-butene isomerization in Ni[P(OEt)3]4–H2SO4 –MeOH system 4885.3.4 Features of the formation and decay of active centers in acrylic derivatives synthesis by the Reppe Method 4905.3.5 Protecting active centers by catalytic process from destruction 4925.3.6 Mechanism of active center formation in Pd(OAc)2 –PPh3 –p-benzoquinone–MeOH catalytic system for alkyne oxidative carbonylation at ≡C–H bond 4945.3.7 Catalysis with small palladium(I) halide and carbonyl halide clusters 4995.3.8 Mechanisms of formation of large cluster complexes and microheterogeneous nanoparticles 5075.3.9 Synthesis and characterization of giant palladium clusters 5125.3.10 Approaches to identification of the nature of catalytically active species in solutions of metal complexes 5135.4 Examples of chain mechanisms and chain carriers of various natures 5185.5 Classification of mechanisms of real catalytic processes 528References 5366 Nonlinear Effects (Critical Phenomena) in Reaction Dynamics in Homogeneous Catalysis with Metal Complexes 5456.1 Historical notes 5486.2 Physicochemical factors responsible for the critical phenomena in homogeneous reactions 5516.2.1 Thermodynamic features of nonequilibrium processes near and far from equilibrium 5526.2.2 Dynamic behavior of systems with linear mechanisms in open reactors with complete mixing 5656.2.3 Nonlinearity of kinetic models 5706.2.4 Main principles and methods of analysis of the dynamic behavior of nonlinear systems 5736.3 Analysis of simple nonlinear kinetic models 5826.4 Mechanisms of oscillatory catalytic reactions 6306.4.1 Belousov–Zhabotinskii reaction (BZ reaction) 6306.4.2 Liquid-phase oxidation of organic compounds by oxygen in Co(OAc)2–Br–CH3COOH system 6406.4.3 Oxidative carbonylation of alkynes in solutions of palladium complexes 644References 6587 Rational Strategy for Designing Kinetic Models and Studying Complex Reaction Mechanisms 6657.1 Stages in the development of chemical kinetics and methodological aspects of the strategy of studying complex reaction mechanisms 6667.2 Alternative strategies for studying complex reaction mechanisms and designing kinetic models 6697.2.1 Traditional strategy 6697.2.2 Rational strategy 6717.3 Hypothesis generation methods and examples 6747.4 Hypothesis generation programs: Application examples and related problems 6777.4.1 Combinatorics on kinetic graphs 6777.4.2 ChemComb (Comb 1) program 6867.4.3 MECHEM program 6917.4.4 NetGen program 6947.4.5 TAMREAC program 6977.4.6 ChemNet program 6977.4.7 Large reaction networks and problems in discrimination of hypotheses and construction of compact kinetic models 713References 7338 Effect of Medium on Reaction Rates in Homogeneous Catalysis with Metal Complexes 7418.1 Effect of electrolytes on the activity coefficients of reaction medium components 7438.2 Effect of electrolytes on the solubility of nonelectrolytes (gases and organic compounds) 7488.3 Effect of electrolytes on the rates of elementary reactions between ions and uncharged substrates 7528.4 Kinetics of catalytic reactions in concentrated aqueous electrolyte (HCl) solutions 7548.5 Organic solvents in homogeneous catalysis with metal complexes 7608.5.1 Main physical and chemical properties of solvents 7608.5.2 Association of solvents and formation of molecular complexes 7638.5.3 Metal complexes in organic and aqueous-organic solvents 7658.5.4 Ion association, ion pairs, and specific salt effect in organic solvents 7718.6 Strong protonic acids in organic solvents and kinetics of catalytic reactions with metal complexes in these media 7758.6.1 Structure and properties of strong acid solutions in organic solvents 7768.6.2 Kinetics of catalytic reactions in HCl–NMP, HCl–C2H5OH, and HCl–C2H5OH–CH3CN systems 7838.7 Ionic liquids in catalytic chemistry 787References 791Conclusion 797Subject Index 801Index of Metals 803Index of Reactions 805