Homogeneous Catalysis with Metal Complexes

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

Oleg Temkin(Autor*in)

Wiley (Verlag)

2. Auflage

Erschienen am 3. Januar 2012

848 Seiten

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Inhalt

Intro
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 p and s 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

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