Homogeneous catalysis with metal complexes kinetic aspects and mechanisms / O.N. Temkin ; translated from the Russian by P.P. Pozdeev.
| Author/creator | Temkin, O. N. |
| Format | Electronic |
| Publication Info | Oxford : Wiley, |
| Description | xx, 806 pages : illustrations ; 25 cm |
| Supplemental Content | Full text available from Ebook Central - Academic Complete |
| Subjects |
| Uniform title | Gomogennyĭ metallokompleksnyĭ kataliz. English |
| Incomplete content | 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 [MARC+73] and [MARC+76] 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 from equilibrium -- 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. |
| Bibliography note | Includes bibliographical references and indexes. |
| Access restriction | Available only to authorized users. |
| Technical details | Mode of access: World Wide Web |
| Genre/form | Electronic books. |
| LCCN | 2023385563 |
| ISBN | 9780470666999 (hbk.) |
| ISBN | 0470666994 (hbk.) |
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| Electronic Resources | Access Content Online | ✔ Available |