Homogeneous Catalysis with Metal Complexes E-Book

Oleg N. Temkin

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 1584

Veröffentlichungsjahr: 2012

Beschreibung

Homogeneous catalysis by soluble metal complexes has gained considerable attention due to its unique applications and features such as high activity and selectivity. Catalysis of this type has demonstrated impressive achievements in synthetic organic chemistry and commercial chemical technology.

Homogeneous Catalysis with Metal Complexes: Kinetic Aspects and Mechanisms presents a comprehensive summary of the results obtained over the last sixty years in the field of the kinetics and mechanisms of organic and inorganic reactions catalyzed with metal complexes.

Topics covered include:

• Specific features of catalytic reaction kinetics in the presence of various mono- and polynuclear metal complexes and nanoclusters
• Multi-route mechanisms and the methods of their identification, as well as approaches to the kinetics of polyfunctional catalytic systems
• Principles and features of the dynamic behavior of nonlinear kinetic models
• The potential, achievements, and limitations of applying the kinetic approach to the identification of complex reaction mechanisms
• The development of a rational strategy for designing kinetic models
• The kinetic models and mechanisms of many homogeneous catalytic processes employed in synthetic and commercial chemistry

Written for specialists in the field of kinetics and catalysis, this book is also relevant for post-graduates engaged in the study

Leseprobe

Table of Contents

Title Page

Copyright

Dedication

Notations and Abbreviations

Preface to English Edition

Preface

Acknowledgments

About the Author

Introduction

References

Chapter 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

1.2 Quasi-steady-state and Quasi-equilibrium Approximations in Chemical Kinetics

1.3 Methods of Graph Theory in Chemical Kinetics and in Theory of Complex Reaction Mechanisms

1.4 Elementary Steps—Selection Rules

References

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

2.1 Mononuclear Metal Complexes

2.2 Polynuclear Complexes in Homogeneous Catalytic and Noncatalytic Reactions

2.3 Catalysis with Polynuclear Copper(I) Halide Complexes in Superconcentrated Solutions

References

Chapter 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

References

Chapter 4: Polyfunctional Catalytic Systems

4.1 Oxidation Reactions of Organic and Inorganic Compounds

4.2 Reactions of Chlorination and Oxidative Chlorination of Organic Compounds

4.3 Oxidative Carbonylation of Organic Compounds

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

References

Chapter 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

5.4 Examples of Chain Mechanisms and Chain Carriers of Various Natures

5.5 Classification of mechanisms of real catalytic processes

References

Chapter 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

6.3 Analysis of Simple Nonlinear Kinetic Models

6.4 Mechanisms of Oscillatory Catalytic Reactions

References

Chapter 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

7.3 Hypothesis Generation Methods and Examples

7.4 Hypothesis Generation Programs: Application Examples and Related Problems

References

Chapter 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

8.6 Strong Protonic Acids in Organic Solvents and Kinetics of Catalytic Reactions with Metal Complexes in These Media

8.7 Ionic Liquids in Catalytic Chemistry

References

Index of Reactions

Index of Metals

Subject Index

This edition first published 2012

© 2012 John Wiley & Sons, Ltd

An earlier version of this work was published in the Russian language by under the title

© Oleg Temkin, 2008

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To My Wife and Friend,

Raisa Vasil'evna Basova,

with Gratitude for Everything

Notations and Abbreviations

Notations:

Areaction affinityaactivity of molecules or ionsanacceptor number of a solvent moleculeBmstoichiometric matrix of reaction mechanismBNstoichiometric submatrix of reaction participantsBpstoichiometric matrix of overall route equationsBXstoichiometric submatrix of intermediatesC±cyclic characteristic of a kinetic graphCAconcentration of substance ACpnweight of nth cycle on pth routeCXconcentration of substance XDiweight of the graph root determinant in ith vertexDikweight of kth rooted tree in ith vertexdndonor number of a solvent moleculeDpnweight of subgraph of nth cycle on pth routeE°standard electrode potentialeeenantiomer excesscomplexity of ith intermediate (ith vertex)FMcomplexity of metal catalystFScomplexity of substrateGmatrix of stoichiometric numbers of stepsGGibbs energyHatomic (molecular) matrixH0Hammet acidity functionh0Hammet acidityInumber of intermediates; ionic strength; induction factor; indicator ratioKreaction equilibrium constantkjreaction rate constantnaverage coordination number; Bjerrum formation functionNnumber of reaction participants (reactants and products)NInumber of linearly independent intermediatesPnumber of linearly independent routes (basis set of routes); pressureQmaxmaximum number of linearly independent reactions (in stoichiometric basis set)Qrnumber of linearly independent overall route equationsrreaction rater(p)reaction rate over pth router±reaction rates in forward ( + ) and reverse (−) directionSnumber of steps in reaction mechanismWjrate on jth steps[X]concentration of substance Xαgas distribution coefficient between gaseous phase and solutionαipolarizability of ith substance (or solvent)stoichiometric coefficient of ith intermediate at jth stepβ12exchange integralχdegree of conversionεsmall parameter; concentration fluctuation; dielectric permittivity ε iextinction coefficientγkinetic chain length; activity coefficientγiactivity coefficient (molar)ηviscosity small parameterμchemical potential; molecularity of step; dipole momentσsurface tensionstoichiometric number of jth step in pth routeξextent of reaction; chemical variableωjweight of jth step

Abbreviations:

AAacrylic acidACacetoneAcacetylacacacetylacetonate (anion)acacHacetylacetoneAcOacetate anionAcOHacetic acidADMAacetaldehyde dimethyl acetal (1,1-dimethoxyethane)ADNadipodinitrileADPadenosine diphosphateAlkalkylAllallylANacetonitrileAPacetophenone (methyl phenyl ketone)ATPadenosine triphosphateBAbutyl acrylateBDMdibutyl dihydromuconateBEE2-bromoethyl ethyl ether (1-bromo-2-ethoxyethane)BGbipartite graph (nonlinear mechanism)BGXsubnetwork of intermediates X in bipartite graphbipy2,2′-bipiridylBME2-bromoethyl methyl ether (1-bromo-2-methoxyethane)[bmim]+1-bityl-3-methylimidazolium cationBPbenzoyl peroxideBQpara-benzoquinoneBubutylButtert-butylBzbenzoylCBchlorobutadieneCHcyclohexeneCHAcyclohexanecarboxylic acidCME2-chloroethyl methyl ether (1-chloro-2-methoxyethane)CSTRcontinuous-flow stirred tank reactorCod1,5-cyclooctadieneCotcyclooctatetraeneCpcyclooctapentadienylCQchloranil (tetrachloro-p-benzoquinone)CVA2-chlorovinylacetylene (2-chloro-1-but-3-ine)Cycyclooctene, cyclohexylDAdiacetylenedbadibenzilydeneacetoneDCAdichloroacetyleneDCE1,2-dichloroethyleneDIOP2,2-dimethyl-4,5-bis(diphenylphosphinomethyl)-1,3-dioxolanDMCdimethyl carbonateDMDAdimethyldiacetyleneDMFdimethylformamideDMOdimethyl oxalateDMSOdimethyl sulfoxidedppe1,2-bis(diphenylphosphin)ethane (diphenylphosphinoethane)dppm1,2-bis(diphenylphosphin)methane (diphenylphosphinomethane)DQduroquinone (tetramethyl-p-benzoquinone)dtcdiethylthiocarbamateDVA1,2-divinylacetyleneEAethyl acetate[emim]+1-ethyl -3-methylimidazolium cationEtethylGAglycolate anionGBLγ-butyrolactoneHalhalogenide (halide)HEhalide ethersHFBhexafluorobenzeneHMPTAhexamethylphosphoric triamideHPhydroperoxideHPAheteropolyacidILionic liquidImimidazoleIPion pairKFkinetic functionKGkinetic graph (subnetwork of intermedites in linear mechanism)KIEkinetic isotope effectLTIlabeled topology identificatorMCAmonochloroacetyleneMCSmulticomponent systemMDAmethyldiacetyleneMemethylMes2,4,6-trimethylphenylMMAmethylmethacrylateMOmolecular orbitalMPmethyl propionateMSAmethanesulfonic acidMSSmultiplicity of steady statesNADHnicotinamide adenine dinucleotideNBDnorbornadieneNCnanoclusterNMPN-methylpyrrolidoneNQpara-naphthoquinoneNunucleophileOcocteneOEPoctaethylporphyrinato anionOlolefineOxoxidantPAphenylacetylenePcphthalocyaninato anionp-cymolpara-cymol (para-methylisopropylbenzene)PEquasi-equilibrium (pre-equilibrium) approximationPEGpolyethylene glycolPFCSpolyfunctional catalytic systemPhphenylPhen1,10-phenanthrolinePipypiperidinePrpropylPypyridineQquinoneRedreductantRNreaction networkSAsuccinic anhydridesalenN, N′-ethylene-bis(salicylideniminato) anionSalophenN, N′-phenylene-bis(salicylideniminato) anionSSquasi-steady-state approximationSSMsimple submechanismTCEtrichlotoethylene; tetrachloroethaneTEMtransmission electron microscopyTHFtetrahydrofuranTItransition-state-topology identificatortmeda1,2-bis(dimethylamino)ethane (tatramethylethylenediamine)TOFcatalyst turnover frequencyTONcatalyst turnover numberTPPtetraphenylporphyrinato anionTStransition stateTsOHpara-toluenesulfonic acidTyrthyrosineVAvinylacetylene monomer; vinyl acetateVCvinyl chloride (1-chloroethylene)VD2-vinyl-1,4-dioxaneVDCvinylidene chloride (1,1-dichloroethylene)XPSX-ray photoelectron spectroscopyXRDX-ray diffractionEpepoxideToltolueneXiintermediate species (intermediates)

Preface to English Edition

In recent years, many books have appeared that are devoted to catalysis—a central, unifying concept in chemistry, including the rapidly developing homogeneous catalysis with metal complexes. This type of catalysis has demonstrated impressive achievements in synthetic organic chemistry and commercial chemical technology.

A reader might be surprised that yet another monograph on catalysis is offered to his or her attention. However, an unbounded field of knowledge such as catalytic chemistry can be considered in various aspects. The present book is aimed at providing a notion about the state-of-the-art in the theory of mechanisms of catalytic reactions in solutions, the state and possibilities of the kinetic method of investigation of the mechanisms of reactions involving metal complexes, a relationship between mechanistic hypotheses and existing kinetic models, and the kinetic models and mechanisms of many homogeneous catalytic processes employed in synthetic and commercial chemistry. Considerable attention in this monograph is devoted to the development of a rational strategy for kinetic models design, to the introduction of new concepts, and to an analysis of problems that are encountered in catalysis with metal complexes (including catalysis with nanoclusters and colloidal particles, homogeneity and heterogeneity of active catalysts, polyfunctional homogeneous catalytic systems, mechanisms of formation and decay of the active centers, chain mechanisms in the catalytic chemistry, allowance for a nonideal character of reaction media, etc.).

The Russian school of chemical kinetics has gained the respect of the world scientific community. It will suffice to mention only works by the Nobel Prize winner N.N. Semenov and other well known scientists such as N.M. Emmanuel', M.I. Temkin, S.Z. Roginskii, G.K. Boreskov, I.I. Moiseev, A.E. Shilov, A.M. Zhabotinskii, S.L. Kiperman, G.S. Yablonskii and A.Ya. Rozovskii. On the other hand, for many reasons, the works of Russian scientists in chemical kinetics (as well as in other fields) only began to regularly appear in international editions in the last 20–25 years. This monograph, generalizing the main results obtained in the field of kinetics and mechanisms of homogeneous catalytic reactions involving metal complexes for the last 60 years, naturally also presents the most interesting investigations performed both in the former USSR and modern Russia.

The author is pleased to know that this book is now available to the whole catalytic community, rather than to Russian-speaking readers only, and is highly grateful to John Wiley & Sons for deciding to publish the English translation of his most recent monograph. This book is a combination of a scientific monograph and a handbook, and the author hopes that it will be useful to specialists as well as to advanced students, graduates, and postgraduates of universities and higher technology colleges by providing a deeper insight into catalytic chemistry, theory of reaction mechanisms, and chemical kinetics of homogeneous catalytic processes.

It is a great pleasure for the author to express his gratitude to Dr P. P. Pozdeev, the translator, for his kind consent to translate this huge monograph from the Russian, creative approach to this work, and fruitful cooperation in all stages of translation manuscript preparation.

O. N. Temkin

Preface

This book is an attempt to summarize the results of an approximately 60 year-long period in which the kinetic method was applied to investigations of the mechanisms of homogeneous catalytic reactions catalyzed by metal complexes. This period of time simultaneously featured both the establishment of homogeneous catalysis with metal complexes as one of the most important directions in catalytic chemistry and the development of a kinetic method and the corresponding approach to studying reaction mechanisms and constructing kinetic models of catalytic processes.

The theory of mechanisms of homogeneous catalytic reactions, including an analysis of the results of investigations of the structure of intermediates and the possible ways to their formation and transformation, noticeably outstrips possibilities of the experimental identification of the mechanisms of particular catalytic processes. Indeed, at the beginning of the 1950s, it was difficult to formulate even a single non-contradictory hypothesis concerning a possible mechanism of one or another catalytic reaction, whereas now the topical problem is how to perform discrimination of numerous probable, theoretically justified hypotheses. Both possibilities and limitations of the kinetic method have become evident. Consideration of the entire set of questions related to the kinetic aspects of homogeneous catalysis with metal complexes is the subject of this monograph.

Despite the great significance of catalysis with metal complexes in both commercial chemistry and organic synthesis, peculiarities and problems in the kinetics of homogeneous catalytic reactions in solutions of metal complexes—in contrast to the kinetics of gas-phase, enzymatic, and heterogeneous catalytic and topochemical reactions—are inadequately reflected in both basic monographs and teaching handbooks.

An analysis of the available literature, including monographs on separate types of catalytic reactions, and his own half-a-century experience led the author to the conclusion that writing a special monograph on the kinetics of catalytic reactions with metal complexes is expedient. This book presents a generalization of the results of studying the kinetics of various homogeneous catalytic (and, in some cases, noncatalytic) processes, which have been obtained since the beginning of 1950s for the reactions in solutions of both transition and nontransition metal complexes.

Traditionally, the kinetics of complex chemical reactions was developed within the framework of adjacent disciplines such as physical chemistry, chemical physics, and biophysics. Modern chemical kinetics can also be considered as a direction in the rapidly developing faculty of mathematical chemistry. Indeed, the direction in mathematical chemistry devoted to the kinetics analyzes the structure and dynamic properties of some special types of differential and algebraic equations. The first issue of a special international journal devoted to mathematical chemistry (Journal of Mathematical Chemistry) was published in 1987.

It is conventional that chemists employ the kinetic method for studying the reaction mechanisms, whereas mathematicians are engaged to solve the inverse problem of chemical kinetics (i.e., to estimate rate constants and parameters of kinetic models and assess the possibility of their identification), analyze the dynamical behavior of the system of differential equations, etc. The optimum situation would naturally imply a collaboration of chemists and mathematicians but, as the author's experience shows, their effective cooperation is hardly possible for many reasons. In this context, one of the author's goals is to concisely present in this book, intended mostly for chemists, the main mathematical approaches, ideas and problems that are important to understand when setting a kinetic experiment, discriminating hypotheses, and interpreting kinetic data. It is hoped that this book will also suggest interesting research objects to specialists engaged in numerical simulations and mathematical chemistry.

The monograph considers the potential, achievements, and limitations of applying the kinetic approach to the identification of mechanisms of complex reactions and dwells on the issues of a rational strategy in constructing theoretically justified kinetic models. The kinetics of reactions in systems with associates and polynuclear complexes of metals is considered in detail. Factors that account for a multi-route character and a relationship between the topological structure of mechanisms and features of kinetic models are analyzed. The problem of kinetic and thermodynamic conjugation in complex reaction kinetics is discussed. Information on the basic principles and specific features of the dynamic behavior of nonlinear kinetic models (including mechanisms of oscillatory reactions) is presented and the thermodynamic, chemical, and mathematical principles of nonlinear dynamics are considered. In addition to data on the mechanisms of well-known processes such as the Belousov–Zhabotinskii reactions, the book presents the results of studying the oscillatory reactions of oxidative carbonylation of alkynes in solutions of palladium complexes, which were discovered in the Department of Chemistry and Technology of Basic Organic Synthesis at the M.V. Lomonosov Moscow State University of Fine Chemical Technology, in the Laboratory of Kinetics and Catalysis headed by the author. The monograph briefly considers existing notions about the influence of a reaction medium and a nonideal character of the solutions of electrolytes and metal complexes in aqueous and nonaqueous media on the kinetics of reactions and the equilibrium of complex formation processes. Approaches to the elimination or allowance for these effects in setting kinetic experiments for the discrimination of hypotheses are discussed.

All sections of this book contain the results of original investigations that have not been considered previously in scientific monographs or teaching handbooks. In Chapters 1, 6, and 8, significant emphasis is placed on teaching aspects, whereas Chapters 2–5 and 7 mostly tend towards a scientific research character, although they can also serve as an additional teaching guide for advanced students, graduates, postgraduates and young specialists engaged in catalysis with metal complexes, complex reaction kinetics, and the theory of mechanisms of catalytic reactions.

O. N. Temkin

Acknowledgments

For my interest in catalysis with metal complexes, catalytic chemistry of alkynes, and kinetic methods of investigation, I am greatly indebted to Professor R. M. Flid—my teacher and friend for 20 years (1954–1974). Professor Flid was a student of Professor M.I. Usanovich (academician of the Kazakh Academy of Sciences) and Professor M.Ya. Kagan, and my meetings with Professor Usanovich for 18 years were an important school that significantly influenced my chemical outlook (see collection of memories Vospominaniya o Professore R.M. Flide [Remembering Professor R.M. Flid], Ekonomika, Moscow, 2006).

I am pleased to heartily express my acknowledgement to Professor I.I. Moiseev, academician of the Russian Academy of Sciences, for highly fruitful and stimulating contacts over more than 50 years.

Writing this book would be impossible without many years of collaboration and fruitful discussions with my co-workers, colleagues, and postgraduate students whose results are also reflected in this monograph. These are Professor G.K. Shestakov, S.M. Brailovskii (Cand.Sci), Professor L.G. Bruk, Professor O.L. Kaliya, Professor D.G. Bonchev (Bulgaria), A.V. Zeigarnik (Cand.Sci), Dr R.E. Val'des-Peres (USA), Professor D. Kamenski (Bulgaria), Professor M.G. Mys'kiv (Ukraine) and Candidates of Sci. N.F. Alekseeva, S.M. Airyan, I.V. Bozhko, V.S. Vartanyan, N.Yu. Vsesvyatskaya (Kozlova), E.G. Gel'perina, S.N. Gorodskii, G.V. Emel'yanova, I.A. Esikova, L.N. Zhir-Lebed', L.A. Zakharova, T.T. Zung, A.S. Zakieva (Abdullaeva), L.A. Il'ina,, A.P. Kozlova, A.V. Kulik, A.E. Kuz'min, O.V. Marshakha, N.G. Mekhryakova, L.Ya. Mesh, F.B.O. Nazarov, A.N. Nyrkova, D.I. Otaraku, I.V. Oshanina, S.A. Panova, A.B. Svetlova (Pshenichnikova), L.V. Reshetnikova (Mel'nikova), L.A. Sil'chenko, M. Skumov, T.G. Sukhova, G.F. Tikhonov, I.V. Trofimova, A.A. Khorkin, Kh.Kh. Man', M.S. Shlapak, G.M. Shulyakovskii, L.V. Shchel'tsyn, and L. Elefteriu A.I. and PhD A.I. Kozlov.

I would like to express my deep gratitude to all of them.

I would like to thank S.M. Brailovskii for kindly permitting the use (in Chapters 1–3) of some materials from our manuscript, written in cooperation (1974) but yet unpublished, devoted to the kinetics of reactions in catalysis with metal complexes and to B.M. Mykhalichko and M.G. Mys'kin for kindly permitting the use of materials from our joint review on polynuclear copper(I) complexes.

I would like to gratefully mention E.D. German, my first supervised diploma student and friend, for that work marked the beginning of potentiometric investigations in situ for catalytic reactions in solutions of Cu(I, II), Ag(I), Hg(II), and Pd(I, II) complexes.

I am also heartily grateful to L.G. Bruk—my student, colleague and friend—for permanent and highly fruitful discussions of all aspects related to catalysis with metal complexes and the entire content of this monograph.

I would like to thank Yu.A. Pisarenko. N.B. Librovich, I.S. Kislina, and A.V. Zeigarnik for kindly reading separate chapters of this book and making highly valuable remarks, and to A.V. Kulik and A.P. Ivanov for their help in preparing the manuscript.

I would like to express my gratitude to D.K. Novikova, editor of the book, for her informal, constructive, and kind cooperation in carrying out a huge work on the manuscript preparation.

Finally, I am grateful to the Russian Foundation for Basic Research for financial support to publishing this book.

O. N. Temkin

About the Author

O. N. Temkin, the author of the monograph Homogeneous Catalysis with Metal Complexes: Kinetic Aspects and Mechanisms, is a well-known specialist in the field of chemical kinetics, catalysis with metal complexes, chemistry of alkynes, and mathematical chemistry. He is a professor of the M.V. Lomonosov Moscow State Institute of Fine Chemical Technology (now the M.V. Lomonosov Moscow State University of Fine Chemical Technology).

Professor Temkin is the co-author of three monographs and two chapters in monographs:

O. N. Temkin and R. M. Flid, Kataliticheskie prevrashcheniya atsetilenovykh soedinenii v rastvorakh kompleksov metallov (Catalytic Transformations of Alkynes in Solutions of Metal Complexes), Nauka, Moscow, 1968.O. N. Temkin, G. K. Shestakov and Yu. A. Treger, Atsetilen: khimiya, mekhanizmy reaktsii, tekhnologiya (Acetylene: Chemistry, Reaction Mechanisms, Technology), Khimiya, Moscow, 1991.O. N. Temkin, A. V. Zeigarnik and D. G. Bonchev, Chemical Reaction Networks. A Graph-Theoretical Approach, CRC Press, Boca Raton, Fl., USA, 1996.O. N. Temkin and D. Bonchev, in Mathematical Chemistry Series, Vol. 2. Chemical Graph Theory. Reactivity and Kinetics, D. Bonchev and D. H. Rouvray (Eds), Abacus Press–Gordon & Breach Sci. Publ., Philadelphia, 1992.O. N. Temkin, A. V. Zeigarnik and D. G. Bonchev, Understanding Chemical Reactivity, Vol. 9, Graph Theoretical Approaches to Chemical Reactivity, D. Bonchev and O. Mekenyan (Eds), Kluwer Academic Publishers, Dordrecht, 1994.

Professor Temkin is the author and co-author of more than 380 scientific publications, including reviews and a chapter (O. Temkin and L. Bruk, Oxidative Carbonylation: Homogeneous) in the Encyclopedia of Catalysis, I. Horvath (Ed.), John Wiley & Sons, 2003, Vol. 5, pp. 394–424. He is the author of article “Homogeneous Catalysis” in the new Big Russian Encyclopedia (Rossiiskaya Entsiklopediya, Moscow, 2007), Vol. 7. His works have been reported in many international scientific journals, including 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., Math. Chem., J. Comput. Chem., J. Mol. Structure (Theochem), and in a number of Russian journals.

Professor Temkin designed for the first time kinetic models of numerous catalytic reactions of alkynes in superconcentrated Cu(I) chloride complex solutions, kinetic models of oxidation, oxidative carbonylation, and chlorination reactions of olefins, dienes, alkynes, and alcohols. He established catalytic systems for the anti-Markovnikov addition of water and hydrogen chloride molecules to alkynes, developed the catalytic chemistry of Pd(I) complexes, discovered a new type of oscillatory reaction in Pd-catalyzed carbonylation of alkynes and many other catalytic systems, and reactions catalyzed by metal complexes.

Introduction

The second half of the 20th century was marked in catalytic chemistry by an extensive development and effective use of catalysts based on metal complexes for homogeneous processes in chemical industry [17]. Since then, metal complex catalysts have become an important tool in modern synthetic organic chemistry [812], while their investigation provided a basis for ideas concerning the mechanisms of reactions in heterogeneous catalysis [1316]. Academician I.I. Moiseev pointed out that “catalysis with metal complexes is an integral part of the scientific-technological revolution in the 20th century” [17].

At the end of the 19th century – i.e., much later than when K.S. Kirchhoff carried out his works on the acid catalysis of potato starch hydrolysis (1811) – three new directions were established in homogeneous catalysis [18, 19]. The use of aluminum complexes as catalysts for the alkylation and acylation of aromatic compounds by Ch. Friedel and J.M. Crafts in 1887 initiated the development of homogeneous electrophilic aprotic catalysis (AlCl3, SnCl4, SbCl5, FeCl3, etc.). A boost to investigations into the reduction–oxidation (redox) reactions with the participation of H2O2 and ROOH catalyzed by metal complexes was provided in 1894 by the work of G.J. Fenton on the oxidation of tartaric acid by dihydroperoxide in Fe(II) salt solution (now known as the Fenton reaction and reagent).

In continuation of the works performed by E. Linnemann, K.M. Zaitsev, and G.N. Glinskii in 1866–1867 [20], which discovered the hydrolysis of propenyl bromide and vinyl bromide in the presence of mercury acetate via the following scheme:

M.G. Kucherov (Kutscheroff) in 1881 suggested that the formation of carbonyl compounds in this reaction is due to the elimination of HBr from alkenyl bromide and the addition of H2O to the intermediate alkyne. Although Kucherov's hypothesis was incorrect, the idea that Hg(II) salts catalyze the hydration of alkynes was successfully confirmed. This discovery, having drawn considerable interest from commercial chemistry, together with the aforementioned works by Linnemann, Zaitsev, and Glinskii, can be considered as triggering the development of the catalysis of organic reactions by complexes of post-transition (Cu, Ag, Au, Hg) and transition metals, involving the formation of organometallic intermediate compounds. Subsequently, it was demonstrated that Hg(II) complexes possess the properties of typical aprotic acids and exhibit some features characteristic of platinum-group metals. The method of acetaldehyde synthesis was patented in 1910 (one year before the death of Kucherov), while the first commercial production of acetaldehyde via the Kucherov reaction was launched in Germany and Canada in 1916. At the same time, it was found by F. Klatte in 1913 that mercury salts in solution are capable of catalyzing the addition of acetic acid to acetylene with the formation of vinyl acetate and ethylidene diacetate, and the addition of HCl to acetylene with the formation of vinyl chloride [21].