Catalysis without Precious Metals

Written for chemists in industry and academia, this ready reference and handbook summarizes recent progress in the development of new catalysts that do not require precious metals. The research thus presented points the way to how new catalysts may ultimately supplant the use of precious metals in some types of reactions, while highlighting the remaining challenges. An essential copanion for organic and catalytic chemists, as well as those working with/on organometallics and graduate students. From the contents: * Catalysis Involving the H' Transfer Reactions of First-Row Transition Metals * Catalytic Reduction of Dinitrogen to Ammonia by Molybdenum Complexes * Molybdenum and Tungsten Catalysts for Hydrogenation, Hydrosilylation and Hydrolysis * Iron in Catalytic Alkene and Carbonyl Hydrogenation Reactions * Olefin Oligomerizations and Polymerizations Catalyzed by Iron and Cobalt Complexes * Cobalt and Nickel Catalyzed Reactions Involving C-H and C-N Activation Reactions * Development of Molecular Electrocatalysts for H2 Oxidation and Production Based on Inexpensive Metals * Nickel-Catalyzed Reductinve Couplings and Cyclizations * Copper-Catalyzed Ligand Promoted Ullmann-Type Coupling Reactions * Copper-Catalyzed Azide-Alkyne Cycloaddition * "Frustrated Lewis Pairs": A Metal-Free Strategy for Hydrogenation Catalysis

Table of Contents:
Preface CATALYSIS INVOLVING THE H*TRANSFER REACTIONS OF FIRST-ROW TRANSITION METALS H*Transfer Between M-H Bonds and Organic Radicals H*Transfer Between Ligands and Organic Radicals H*Transfer Between M-H and C-C Bonds Chain Transfer Catalysis Catalysis of Radical Cyclizations Competing Methods for the Cyclization of Dienes Summary and Conclusions CATALYYTIC REDUCTION OF DINITROGEN TO AMMONIA BY MOLYBDENUM Introduction Some Characteristics of Triamidoamine Complexes Possible [HIPTN3N]Mo Intermediates in a Catalytic Reduction of Molecular Nitrogen Interconversion of Mo(NH3) and Mo(N2) Catalytic Reduction of Dinitrogen MoH and Mo(H2) Ligand and Metal Variations Comments MOLYBDENUM AND TUNGSTEN CATALYSTS FOR HYDROGENATION, HYDROSILYLATION AND HYDROLYSIS Introduction Proton Transfer Reactions of Metal Hydrides Hydride Transfer Reactdions of Metal Hydrides Stoichiometric Hydride Transfer Reactivity of Anionic Metal Hydride Complexes Catalytic Hydrogenation of Ketones with Anionic Metal Hydrides Ionic Hydrogenation of Ketones Using Metal Hydrides and Added Acid Ionic Hydrogenations from Dihydrides: Delivery of the Proton and Hydride from One Metal Catalytic Ionic Hydrogenations With Mo and W Catalysts Mo Phosphine Catalysts With Improved Lifetimes Tungsten Hydrogenation Catalysts with N-Heterocyclic Carbene Ligands Catalysts for Hydrosilylation of Ketones Cp2Mo Catalysts for Hydrolysis, Hydrogenations and Hydrations Conclusion MODERN ALCHEMY: REPLACING PRECIOUS METALS WITH IRON IN CATALYTIC ALKENE AND CARBONYL HYDROGENATION REACTIONS Introduction Alkene Hydrogenation Carbonyl Hydrogenation Outlook OLEFIN OOLIGOMERIZATIONS AND POLYMERIZATIONS CATALYZED BY IRON AND COBALT COMPLEXES BEARING BIS(IMINO)PYRIDINE LIGANDS Introduction Precatalyst Synthesis Precatalyst Activation and Catalysis The Active Catalyst and Mechanism Other Applications Conclusions and Outlook COBALT AND NICKEL CATALYZED REACTIONS INVOLVING C-H AND C-N ACTIVATION REACTIONS Introduction Catalysis with Cobalt Catalysis with Nickel A MODULAR APPROACH TO THE DEVELOPMENT OF MOLECULAR ELECTROCATALYSTS FOR H2 OXIDATION AND PRODUCTION BASED ON INEXPENSIVE METALS Introduction Concepts in Catalyst Design Based on Structural Studies of Hydrogenase Enzymes A Layered or Modular Approach to Catalyst Design Using the First Coordination Sphere to Control the Energies of Catalytic Intermediates Using the Second Coordination Sphere to Control the Movement of Protons between the Metal and the Exterior of the Molecular Catalyst Integration of the First and Second Coordination Spheres Summary NICKEL-CATALYZED REDUCTIVE COUPLINGS AND CYCLIZATIONS Introduction Couplings of Alkynes with alpha, beta-Unsaturated Carbonyls Couplings of Alkynes with Aldehydes Conclusions and Outlook COPPER-CATALYZED LIGAND PROMOTED ULLMANN-TYPE COUPLING REACTIONS Introduction C-N Bond Formation C-O Bond Formation C-C Bond Formation C-S Bond Formation C-P Bond Formation Conclusion COPPER-CATALYZED LIGAND PROMOTED ULLMANN-TYPE COUPLING REACTIONS Introduction C-N Bond Formation C-O Bond Formation C-C Bond Formation C-S Bond Formation C-P Bond Formation Conclusion COPPER-CATALYZED AZIDE-ALKYNE CYCLOADDITION (CuAAC) Introduction Azide-Alkyne Cycloaddition: Basics Copper-Catalyzed Cycloadditions "FRUSTRATED LEWIS PAIRS": A METAL-FREE STRATEGY FOR HYDROGENATION CATALYSIS Phosphine-Borane Activation of H2 "Frustrated Lewis Pairs" Metal-Free Catalytic Hydrogenation Future Considerations

About the Author :
After 21 years at Brookhaven National Laboratory in Long Island, New York, Morris Bullock moved to Pacific Northwest National Laboratory in 2006, where he is a Laboratory Fellow, as well as Director of the Center for Molecular Electrocatalysis. Dr. Bullock's research interests focus on reactivity of metal hydrides, including proton transfer, hydride transfer, and hydrogen atom transfer reactions, and on the development of molecular catalysts for the oxidation of hydrogen and production of hydrogen.

Review :
“In summary, this timely and detailed book brings the subject right up to date, with chapters from international leaders in the areas discussed, and should be read by everyone who works on homogeneous catalysis – not only those who might be looking carefully at their reagent procurement costs, but in particular those who might be looking for some exciting new intellectual challenges for scientific investigation. Highly recommended.”  (Applied Organometallic Chemistry, 1 July 2015) "In summary, this monograph gives a good overview on the present state of the art in applying non-precious metal catalysts for a variety of applications. This is a fast moving area of research and for some reactions even better results have been produced in the last one or two years. This does by no means detracts from the value of this monograph, but indicates that the future of the field might look even brighter." (ChemCatChem, 2011) "However, that is unlikely to put off the target audience for whom this book would be useful as a library resource, to dip into as and when needed, rather than an essential read for researchers in this field". (Chemistry World, 1 May 2011) "The 306-page hardcover book summarizes recent progress in the field, pointing to how new catalysts may ultimately supplant precious metals in some types of reactions. Also, the book goes on to highlight the remaining chemical challenges and areas in need of further study". (Fuel Cell Works, 21 December 2010) "A new book edited by Dr. Morris Bullock of Pacific Northwest National Laboratory summarizes the progress and challenges of designing catalysts from less expensive, more abundant metals . . . also, the book goes on to highlight the remaining chemical challenges and areas in need of further study. The book was written by experts from the United States, Canada, the United Kingdom and China." (Technology Today, 20 December 2010)