Metal carbene complexes have made their way from organometallic curiosities to valuable reagents and catalysts. They offer novel synthetic opportunities in carbon-carbon bond formation based on either carbene-centered reactions or on metal-templated processes which makes them indispensable in modern synthetic methodology. The most prominent metal carbenes are now either commercially available or easy to synthesize and handle with modern laboratory techniques. This volume organized in eight chapters written by the leading scientists in the field illustrates the theoretical background, non-classical nucleophilic and cycloaddition patterns, chromium-templated benzannulation and photo-induced reactions, rhodium-catalyzed carbene transfer as well as the principles and applications of olefin metathesis which has coined the progress in synthetic methodology over the past decade. Designed for researchers in academia and industry as well as graduate students it presents the state-of-the-art potential of carbene complexes in modern organic synthesis.

V.W.-W. Yam, K.M.-C. Wong: Luminescent Molecular Rods - Transition Metal Alkynyl Complexes.- D.K. James, M. Tour: Molecular Wires.- C. Chiorboli, M.T. Indelli, F. Scandola: Photoinduced Electron/Energy Transfer Across Molecular Bridges in Binuclear Metal Complexes.- E.A. Weiss, M.R. Wasielewski, M.A. Ratner: Molecules as Wires: Molecule-Assisted Movement of Charge and Energy.- F.C. Grozema, L.D.A. Siebbeles, G.H. Gelinck, J.M. Warman: The Opto-Electronic Properties of Isolated Phenylenevinylene Molecular Wires

Johannes G. de Vries: Pd-catalyzed coupling reactions.- Gregory T. Whiteker and Christopher J. Cobley: Applications of Rhodium-Catalyzed Hydroformylation in the Pharmaceutical, Agrochemical and Fragrance Industries.- Philippe Dupau: Ruthenium-catalyzed Selective Hydrogenation for Flavor and Fragrance Applications.- Hans-Ulrich Blaser, Benoit Pugin and Felix Spindler: Asymmetric Hydrogenation.- Ioannis Houpis: Case Study: Sequential Pd-catalyzed Cross-Coupling Reactions; Challenges on Scale-up.- Adriano F. Indolese: Pilot Plant Scale Synthesis of an Aryl-Indole - Scale up of a Suzuki Coupling.- Per Ryberg: Development of a Mild and Robust Method for Palladium Catalysed Cyanation on Large Scale.- Cheng-yi Chen: Application of Ring Closing Metathesis Strategy to the Synthesis of Vaniprevir (MK-7009), a 20-Membered Macrocyclic HCV Protease Inhibitor.

Valentine P. Ananikov, Irina P. Beletskaya: Alkyne and alkene insertion into metal-heteroatom and metal-hydrogen bonds - the key stages of hydrofunctionalization process.- Akihiko Ishii* and Norio Nakata: The Mechanism for Transition Metal-Catalyzed Hydrochalcogenation of Unsaturated Organic Molecules.- A. L. Reznichenko and Kai C. Hultzsch: Early Transition Metal (Group 3-5, Lanthanides and Actinides) and Main Group Metal (Group 1, 2, and 13) Catalyzed Hydroamination.- Naoko Nishina and Yoshinori Yamamoto: Late transition metal catalyzed hydroamination.- Sumod A. Pullarkat and Pak-Hing Leung: Chiral Metal Complex Promoted Asymmetric Hydrophosphinations.- Masato Tanaka: Recent Progress in Transition Metal-Catalyzed Addition Reactions of H-P(O) Compounds with Unsaturated Carbon Linkages.- Christian Bruneau: Group 8 metals-catalyzed O-H bond addition to unsaturated molecules.- Giorgio Abbiati, Egle M. Beccalli, Elisabetta Rossi: Groups 9 and 10 metals-catalyzed O-H bond addition to unsaturated molecules.- Nuria Huguet and Antonio M. Echavarren: Gold-Catalyzed O-H Bond Addition to Unsaturated Organic Molecules.- Akiya Ogawa: Transition-Metal-Catalyzed S-H and Se-H Bonds Addition to Unsaturated Molecules.

Organometallic Ion Chemistry features eight chapters, written by acknowledged authorities, covering the gas-phase chemistry of organometallic ions. Topics covered include: periodic trends in gas-phase thermochemistry of transition metal-ligand systems; ab initio calculations to determine electronic structure, geometric structure, and thermochemistry of metal-containing systems; electronic state effects on metal ion reactivity; organometallic ion photochemistry; applications of gas-phase electron transfer equilibria in organometallic redox thermochemistry. Also included are state of the art mass spectrometric instrumentation used in such studies. Finally, the book features - for the first time in one place - a comprehensive list (containing over 1500 entries) of metal ion-ligand bond energies, obtained from theory and experiment. An invaluable reference source for ion chemists, organometallic chemists and surface chemists, at both expert and graduate student levels.

T. L.S. Kishbaugh: Metalation of Pyrrole.- K.-S. Yeung: Furans and Benzofurans.- P. E. Alford: Lithiation-Based and Magnesation-Based Strategies for the Functionalization of Imidazole: 2001-2010.- L. Fu: Metalation of Oxazoles and Benzoxazoles.- S. Roy * S. Roy * G. W. Gribble: Metalation of Pyrazoles and Indazoles.- J. C. Badenock: Metalation Reactions of Isoxazoles and Benzisoxazoles.- Y.-J. Wu: Thiazoles and Benzothiazoles.- C. F. Nutaitis: Isothiazoles and Benzisothiazoles.- E. R. Biehl: Recent Advances in the Synthesis of Thiophenes and Benzothiophenes.- J. M. Lopchuk: Mesoionics.- J. M. Lopchuk: Azoles with 3-4 Heteroatoms.

Our knowledge of the chemistry of selenium and tellurium has seen significant progress in the last few decades. This monograph comprises contributions from leading scientists on the latest research into the synthesis, structure and bonding of novel selenium and tellurium compounds. It provides insight into mechanistic studies of these compounds and describes coordination chemistry involving selenium and tellurium containing ligands. Contributions also describe the theoretical and spectroscopic studies of selenium and tellurium compounds. Additionally, this monograph outlines the applications of selenium and tellurium in biological systems, materials science and as reagents in organic synthesis and shows how these applications have been a fundamental driving force behind the research into the inorganic and organic chemistry these fascinating elements.

Adi Haber's thesis summarises the use of a new entity, the corrole, to combat one of the major cardiovascular diseases, atherosclerosis. She examines the effects of three rationally designed corrole-metal complexes on some of the many variables which contribute to the development of atherosclerosis. There is a focus on both the "bad" and "good" cholesterol carriers, LDL and HDL. Adi Haber proceeds from basic findings in pure chemistry through biochemical and cell culture tests to in vivo examinations. The work in this thesis shows that corroles are highly efficient both for early and late treatment of atherosclerosis in animals. These results will pave the way for ongoing regulated preclinical studies focussed on the development of metallocorroles as potential drugs for treating cardiovascular diseases.

Lucas Montero de Espinosa and Michael A. R. Meier: Olefin Metathesis of Renewable Platform Chemicals.- Pieter C. A. Bruijnincx, Robin Jastrzebski, Peter J. C. Hausoul, Robertus J. M. Klein Gebbink, and Bert M. Weckhuysen: Pd-Catalysed Telomerisation of 1,3-Dienes with Multifunctional Renewable Substrates - Versatile Routes for the Valorisation of Biomass-Derived Platform Molecules.- A Behr, A. J. Vorholt: Hydroformylation and related reactions of renewable resources.- Ties J. Korstanje, Robertus J.M. Klein Gebbink: Catalytic oxidation and deoxygenation of renewables with rhenium complexes.- Antoine Buchard, Clare M. Bakewell, Jonathan Weiner and Charlotte K. Williams: Recent Developments In Catalytic Activation Of Renewable Resources For Polymer Synthesis.

Gerard van Koten: The Mono-anionic ECE-Pincer Ligand - a Versatile Privileged Ligand Platform: General Considerations.- Elena Poverenov, David Milstein: Non-Innocent Behavior of PCP and PCN Pincer Ligands of Late Metal Complexes.- Dean M. Roddick: Tuning of PCP Pincer Ligand Electronic and Steric Properties.- Gemma R. Freeman, J. A. Gareth Williams: Metal Complexes of Pincer Ligands: Excited States, Photochemistry, and Luminescence.- Davit Zargarian, Annie Castonguay, Denis M. Spasyuk: ECE-Type Pincer Complexes of Nickel.- Roman Jambor and Libor Dostal: The Chemistry of Pincer Complexes of 13 - 15 Main Group Elements.- Kalman J. Szabo: Pincer Complexes as Catalysts in Organic Chemistry.- Jun-ichi Ito and Hisao Nishiyama: Optically Active Bis(oxazolinyl)phenyl Metal Complexes as Multi-potent Catalysts.- Anthony St. John, Karen I. Goldberg, and D. Michael Heinekey: Pincer Complexes as Catalysts for Amine Borane Dehydrogenation.- Dmitri Gelman and Ronit Romm: PC(sp3)P Transition Metal Pincer Complexes: Properties and Catalytic Applications.- Jennifer Hawk and Steve Craig: Physical Applications of Pincer Complexes.

Bismuth Catalysts in Aqueous Media, by Shu Kobayashi, Masaharu Ueno and Taku Kitanosono.- Pentavalent Organobismuth Reagents in Organic Synthesis: Alkylation, Alcohol Oxidation and Cationic Photopolymerization , by Yoshihiro Matano.- Environmentally Friendly Organic Synthesis Using Bismuth(III) Compounds, by Scott W. Krabbe and Ram S. Mohan.- Bismuth-Catalyzed Addition of Silyl Nucleophiles to Carbonyl Compounds and Imines, by Thierry Ollevier.- Bismuth Salts in Catalytic Alkylation Reactions, by Magnus Rueping and Boris J. Nachtsheim.- New Applications for Bismuth(III) Salts in Organic Synthesis: From Bulk Chemicals to Steroid and Terpene Chemistry, by J. A. R. Salvador, S. M. Silvestre, R. M. A. Pinto, R. C. Santos and C. Le Roux.- Cationic Bismuth-Catalyzed Hydroamination and Direct Substitution of the Hydroxy Group in Alcohols with Amides, by Shigeki Matsunaga and Masakatsu Shibasaki.- Transition-Metal Catalyzed C-C Bond Formation Using Organobismuth Compounds, by Shigeru Shimada and Maddali L. N. Rao.- Bismuth(III) Salts as Synthetic Tools in Organic Transformations, by J. S. Yadav, Aneesh Antony and Basi V. Subba Reddy.

Silicones have unique properties including thermal oxidative stability, low temperature flow, high compressibility, low surface tension, hydrophobicity and electric properties. These special properties have encouraged the exploration of alternative synthetic routes of well defined controlled microstructures of silicone copolymers, the subject of this Springer Brief. The authors explore the synthesis and characterization of notable block copolymers. Recent advances in controlled radical polymerization techniques leading to the facile synthesis of well-defined silicon based thermo reversible block copolymers are described along with atom transfer radical polymerization (ATRP), a technique utilized to develop well-defined functional thermo reversible block copolymers. The brief also focuses on Polyrotaxanes and their great potential as stimulus-responsive materials which produce poly (dimethyl siloxane) (PDMS) based thermo reversible block copolymers.

Giovanni Poli, Guillaume Prestat, Frederic Liron, Claire Kammerer-Pentier: Selectivity in Palladium Catalyzed Allylic Substitution.- Jonatan Kleimark and Per-Ola Norrby: Computational Insights into Palladium-mediated Allylic Substitution Reactions.- Ludovic Milhau, Patrick J. Guiry: Palladium-catalyzed enantioselective allylic substitution.- Wen-Bo Liu, Ji-Bao Xia, Shu-Li You: Iridium-Catalyzed Asymmetric Allylic Substitutions.- Christina Moberg: Molybdenum- and Tungsten-Catalyzed Enantioselective Allylic Substitutions.- Jean-Baptiste Langlois, Alexandre Alexakis: Copper-catalyzed enantioselective allylic substitution.- Jeanne-Marie Begouin, Johannes E. M. N. Klein, Daniel Weickmann, B. Plietker: Allylic Substitutions Catalyzed by Miscellaneous Metals.- Barry M. Trost, Matthew L. Crawley: Enantioselective Allylic Substitutions in Natural Product Synthesis.

Organolithium chemistry occupies a central position in the selective construction of C-C bonds in both simple and complex molecules. Paralleling the surge of interest in methods for asymmetric synthesis, the use of organolithiums in enantioselective synthesis has witnessed spectacular advances in a little over a decade. This volume is the first dedicated to a comprehensive coverage of this important area. It is designed to provide graduate students and researchers with a rich source of essential information on synthesising molecules in an enantioselective manner using organolithiums, and be an inspiration for future developments. Following an overview chapter summarising the key milestones, successive chapters, each written by leading experts in their field, critically survey all the major areas of progress.

to thank Messrs J. R. Sanders, W. E. Lindsell and M. G. Swanwick for helping to check the text and references and prepare indexes. Finally, I should like to thank my wife for the very considerable assis tance she has given me in the writing and production of this book. M. L. H. G. Contents Preface to the Third Edition, Volume Two Page v INTRODUCTION TO VOLUME TWO I Oassification I The IS-electron rule 2 (i) The basis of the I8-electron rule p. 4, (ii) Exceptions to the I8-electron rule p. 5 1. TWO-ELECTRON LIGANDS 7 A. Classification 7 B. The preparation of olefin-transition metal complexes 7 (a) Displacement of solvent ligands p. 9, (b) Preparations from metal carbonyls p. 9, (c) Less common preparative routes p. 11, Reductive olefination method p. 12 C. A molecular orbital description of the bonding in orga- metallic complexes 13 (a) General comments p. 13, (b) Symmetry considerations p. 13, (c) Energies of the molecular orbitals p. 14 D. A description of the bonding of 2-electron ligands to transition metals 14 E. General comments of 2-electron ligands 19 (a) Infrared studies p. 20, (b) Effect of olefin substituents p. 21, (c) The rotation of ethylene about the ligand-metal bond p. 22, (d) Chemical properties p. 23 F. Particular complexes of metals with 2-electron ligands 25 (a) Copper, silver and gold p. 25, Complexes with benzene p. 28, (b) Nickel, palladium and platinum p."

The fields of hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) continue to attract the attention of researchers in the various disciplines connected to these fascinating problems that represent two of the key outstanding chemical challenges for the petroleum refining industry in view of their very strong environmental and commercial implications. One area that has flourished impressively over the last 15 years is the organometallic chemistry of thiophenes and other related sulfur-containing molecules. This has become a powerful method for modeling numerous surface species and reactions implicated in HDS schemes, and nowadays it represents an attractive complement to the standard procedures of surface chemistry and heterogeneous catalysis, for understanding the complex reaction mechanisms involved in this process. Similar developments have begun to appear in connection with HDN mechanisms, although in a much more modest scale and depth. Some years ago when, encouraged by Prof. B. R. James, this book was planned, several excellent reviews and monographs treating different aspects of HDS were already available including some on the subject of organometallic models. However, it seemed appropriate to try to summarize the most striking features of this chemistry in an updated and systematic way, and inasmuch as possible in connection with the common knowledge and beliefs of the mechanisms of heterogeneous HDS catalysis. Hopefully, this attempt to build some conceptual bridges between these two traditionally separated areas of chemistry has met with some success.

Computational methods have become an indispensible tool for elucidating the mechanism of organometallic reactions. This snapshot of state-of-the-art computational studies provides an overview of the vast field of computational organometallic chemistry. Authors from Asia, Europe and the US have been selected to contribute a chapter on their specialist areas. Topics addressed include: DFT studies on zirconium-mediated reactions, force field methods in organometallic chemistry, hydrogenation of -systems, oxidative functionalization of unactivated C-H bonds and olefins, the osmylation reaction, and cobalt carbonyl clusters. The breadth and depth of the contributions demonstrate not only the crucial role that computational methods play in the study of a wide range of organometallic reactions, but also attest the robust health of the field, which continues to benefit from, as well as inspire novel experimental studies.

Masakatsu Shibasaki, Motomu Kanai, Shigeki Matsunaga, and Naoya Kumagai: Multimetallic Multifunctional Catalysts for Asymmetric Reactions.- Takao Ikariya: Bifunctional transition metal-based molecular catalysts for asymmetric syntheses.- Chidambaram Gunanathan and David Milstein: Bond Activation by Metal-Ligand Cooperation: Design of Green Catalytic Reactions Based on Aromatization-Dearomatization of Pincer Complexes.- Madeleine C. Warner, Charles P. Casey, and Jan-E. Backvall: Shvo s Catalyst in Hydrogen Transfer Reactions.- Noritaka Mizuno, Keigo Kamata, and Kazuya Yamaguchi: Liquid-Phase Selective Oxidation by Multimetallic Active Sites of Polyoxometalate-Based Molecular Catalysts.- Pingfan Li and Hisashi Yamamoto: Bifunctional Acid Catalysts for Organic Synthesis.- Jun-ichi Ito, Hisao Nishiyama: Bifunctional Phebox Complexes for Asymmetric Catalysis."

While the organometallic chemistry of the d-block transition elements has been a flourishing field for the past 25 years, it has only been in the last several years that dramatic activity and progJ'ess has occurred in the area of lanthanide and actinide organometallic chemistry. The f. -element organometallic research effort has been truly multinational and multidisciplinary. In a large number of countries, sCientists have become increasingly interested in the synthesis, reactivity, spectroscopy, and the molecular and electronic structures of f-element organometallic compounds. The backgrounds of these scientists range from organic, inorganic, nuclear, and catalytic chemistry to chemical and nuclear physics. The motivations for the study of f-element organometallics have been equally varied. In the area of basic research, there has been a growing realization that the lanthanides and actinides represent two unique and, to a great extent, neglected families of elements in which many fascinating aspects of chemistry and bonding remain to be explored. On a more practical level, an increasing number of these elements play important roles in nuclear energy production and in industrial catalytic processes. It has become apparent that efficiency and safety in both areas could greatly benefit from increased knowledge. In the past there has been no suitable international forum available for bringing together researchers in the diverse areas of f-element organometallic science mentioned above.

Structure, Bonding, and Reactivity of Reactant Complexes and Key Intermediates, by Elena Soriano and Jose Marco-Contelles.-

Cycloisomerization of 1, "n"-Enynes Via Carbophilic Activation, by Patrick Yves Toullec and Veronique Michelet.-

DFT-Based Mechanistic Insights into Noble Metal-Catalyzed Rearrangement of Propargylic Derivatives: Chirality Transfer Processes, by Olalla Nieto Faza and Angel R. de Lera.-

"N"-Heterocyclic Carbene Complexes of Au, Pd, and Pt as Effective Catalysts in Organic Synthesis, by Andrea Correa, Steven P. Nolan and Luigi Cavallo.-

Activation of Allenes by Gold Complexes: A Theoretical Standpoint, by Max Malacria, Louis Fensterbank and Vincent Gandon.-

Heterocyclization of Allenes Catalyzed by Late Transition Metals: Mechanisms and Regioselectivity, by Benito Alcaide, Pedro Almendros, Teresa Martinez del Campo, Elena Soriano and Jose Marco-Contelles.-

Gold-Catalyzed Cycloadditions Involving Allenes: Mechanistic Insights from Theoretical Studies, by Sergi Montserrat, Gregori Ujaque, Fernando Lopez, Jose L. Mascarenas and Agusti Lledos.-

"

Kyle A. Grice, Margaret L. Scheuermann and Karen I. Goldberg: Five-Coordinate Platinum(IV) Complexes.- Jay A. Labinger and John E. Bercaw: The Role of Higher Oxidation State Species in Platinum-Mediated C-H Bond Activation and Functionalization.- Joy M. Racowski and Melanie S. Sanford: Carbon-Heteroatom Bond-Forming Reductive Elimination from Palladium(IV) Complexes.- Helena C. Malinakova: Palladium(IV) Complexes as Intermediates in Catalytic and Stoichiometric Cascade Sequences Providing Complex Carbocycles and Heterocycles.- Allan J. Canty and Manab Sharma: h1-Alkynyl Chemistry for the Higher Oxidation States of Palladium and Platinum.- David C. Powers and Tobias Ritter: Palladium(III) in Synthesis and Catalysis.- Marc-Etienne Moret: Organometallic Platinum(II) and Palladium(II) Complexes as Donor Ligands for Lewis-Acidic d10 and s2 Centers.

This book serves as a concise guide to essential topics in Transition Metal Organometallic Chemistry for senior undergraduate and graduate students; it blends qualitative theoretical approach with experimental description of the facts. Its content emphasizes on the orbital description of M-L bonds; the electronic structures of the main types of organometallic complexes (ML2 to ML6); main types of organometallic reactions; organometallic compound synthesis, analytical characterization and the reactivity and lastly the applications of transition metals in homogeneous catalysis.

According to R.H. Crabtree, Metal Dihydrogen and sigma-Bond Complexes is described as 'the definitive account of twentieth-century work in the area of sigma complexation'. It covers not only Kubas' discovery of dihydrogen coordination and the study of its structure and general properties but also discusses both the theoretical beliefs and experimental results of bonding and activation of dihydrogen on metal centers and the coordination and activation of C-H, B-H, X-H, and X-Y bonds, giving an overview of 'one of the hottest areas in chemistry'.

Juan I. Padron and Victor S. Martin: Catalysis by means of Fe-based Lewis acids; Hiroshi Nakazawa*, Masumi Itazaki: Fe-H Complexes in Catalysis; Kristin Schroder, Kathrin Junge, Bianca Bitterlich, and Matthias Beller: Fe-catalyzed Oxidation Reactions of Olefins, Alkanes and Alcohols: Involvement of Oxo- and Peroxo Complexes; Chi-Ming Che, Cong-Ying Zhou, Ella Lai-Ming Wong: Catalysis by Fe=X Complexes (X=NR, CR2); Rene Peters, Daniel F. Fischer and Sascha Jautze: Ferrocene and Half Sandwich Complexes as Catalysts with Iron Participation; Markus Jegelka, Bernd Plietker: Catalysis by Means of Complex Ferrates."

The present book is based on the work of M.N.Bochkarev, G.S.Kalinina, L.N. zakharov and S.Ya.Khorshev. The Russian edition of that book appeared under the same title in 1989 and covered literature data up to the middle of 1986. Since that time the number of publications on this subject increased significantly. In this volume we include all the data published up to the end of 1990, as well as some of the most important relevant articles of 1991. Therefore, this book should be considered as a new book, devoted to the same problems, rather than as just a translation of the mentioned issue. This book deals with compounds of scandium, yttrium, lanthanum and lanthanoids containing direct metal-carbon bond, Le. with the real organometallic complexes of these metals. Besides, the volume includes the rare earth complexes, in which organic ligand is bonded to the metal atom via the atom of another element of the Periodic Table. In other words, the book includes all classes of rare earth organoderivatives. Carboxilates, fl-diketonates and related chelates are the exceptions, because their properties are closer to inorganic compounds and they were fully described elsewhere. It should be noted, that "rare earth elements," "rare earth metals," "lanthanoids" and related terms are used in this book for indicating scandium, yttrium, lanthanum and the following 14 elements of the Periodic Table.