Ruthenium Based Hydrogenation And Frustrated Lewis Pair Chemistry

Since the discovery of catalytic hydrogenation, the field of transition metal-based hydrogenation catalysis has grown significantly. Recently, main group systems have demonstrated the capability to perform some of the same catalytic processes. Frustrated Lewis pairs (FLP), the combination of sterically encumbered Lewis acids and Lewis bases, are able to activate a variety of small molecules. The research presented in this thesis investigates main group and transition metal-based catalytic hydrogenation, as well as stoichiometric transformations with main group systems. A variety of ruthenium N-heterocyclic carbene (NHC) complexes were generated with polyethylene glycol (PEG) on the NHC to impart water-solubility. These hydrogenation catalysts were used to hydrogenate nitrile butadiene rubber (NBR) to hydrogenated nitrile butadiene rubber (HNBR). The PEG lengths had minimal effect on the conversion of NBR in solution phase. For the hydrogenation of NBR latex, a correlation was observed between the PEG length and the activity. A family of phosphinimines with different steric and electronic properties was synthesized from the Staudinger reaction between alkynyl-phosphines and azido-phosphine-boranes. Cyclization of these products can be induced thermally or by the addition of catalytic amounts of B(C6F5)3. Upon cyclization, a net trans-hydroboration was observed on the exocyclic alkene. A novel geminal boron-sulfur FLP was synthesized from the hydroboration of sulfur-alkynes. These systems demonstrated FLP-type chemistry such as the activation of terminal alkynes. Interestingly, the frustration was a result of the steric conflict between the tert-butyl substituent on the carbon and the p-tolyl substituent on the Lewis basic sulfur. This FLP-type reactivity can altered upon isomerization of the complex, forming the classical Lewis pair adduct. Finally, metal-free transformation of 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one was investigated. The Lewis acid B(C6F5)3 was shown to catalytically hydrogenate the allyl functionality of the substrate, as well as catalytic hydrosilylation of the conjugated alkene.

Discovery of Frustrated Lewis Pairs: Intermolecular FLPs for Activation of Small Molecules, by Douglas W. Stephan Intramolecular Frustrated Lewis Pairs: Formation and Chemical Features, by Gerald Kehr, Sina Schwendemann, Gerhard Erker Frustrated Lewis Pair Mediated Hydrogenations, by Douglas W. Stephan, Gerhard Erker Amine-Borane Mediated Metal-Free Hydrogen Activation and Catalytic Hydrogenation, by Victor Sumerin, Konstantin Chernichenko, Felix Schulz, Markku Leskelä, Bernhard Rieger, Timo Repo Hydrogen Activation by Frustrated Lewis Pairs: Insights from Computational Studies, by Tibor András Rokob, Imre Pápai Quantum Chemistry of FLPs and Their Activation of Small Molecules: Methodological Aspects, by Birgitta Schirmer, Stefan Grimme Computational Design of Metal-Free Molecules for Activation of Small Molecules, Hydrogenation, and Hydroamination, by Zhi-Xiang Wang, Lili Zhao, Gang Lu, Haixia Li, Fang Huang Computational Studies of Lewis Acidity and Basicity in Frustrated Lewis Pairs, by Thomas M. Gilbert Solid-State NMR as a Spectroscopic Tool for Characterizing Phosphane - Borane Frustrated Lewis Pairs, by Thomas Wiegand, Hellmut Eckert, Stefan Grimme

Mentioned as the second prize area in his will, Chemistry was the most important science for Alfred Nobel's own work. The development of Nobel's inventions as well as the industrial processes he employed were based upon chemical knowledge. This volume is a collection of the Nobel lectures delivered by the prizewinners, together with their biographies and the presentation speeches for the period 2006 2010. Each Nobel lecture is based on the work for which the laureate was awarded the prize. List of prizewinners and their award citations: (2006) Roger D Kornberg for his studies of the molecular basis of eukaryotic transcription; (2007) Gerhard Ertl for his studies of chemical processes on solid surfaces; (2008) Osamu Shimomura, Martin Chalfie and Roger Y Tsien for the discovery and development of the green fluorescent protein, GFP; (2009) Venkatraman Ramakrishnan, Thomas A Steitz and Ada E Yonath for studies of the structure and function of the ribosome; (2010) Richard F Heck, Ei-ichi Negishi and Akira Suzuki for palladium-catalyzed cross couplings in organic synthesis.

Frustrated Lewis Pairs: From Dihydrogen Activation to Asymmetric Catalysis, by Dianjun Chen, Jürgen Klankermayer Coexistence of Lewis Acid and Base Functions: A Generalized View of the Frustrated Lewis Pair Concept with Novel Implications for Reactivity, by Heinz Berke, Yanfeng Jiang, Xianghua Yang, Chunfang Jiang, Subrata Chakraborty, Anne Landwehr New Organoboranes in "Frustrated Lewis Pair" Chemistry, by Zhenpin Lu, Hongyan Ye, Huadong Wang Paracyclophane Derivatives in Frustrated Lewis Pair Chemistry, by Lutz Greb, Jan Paradies Novel Al-Based FLP Systems, by Werner Uhl, Ernst-Ulrich Würthwein N-Heterocyclic Carbenes in FLP Chemistry, by Eugene L. Kolychev, Eileen Theuergarten, Matthias Tamm Carbon-Based Frustrated Lewis Pairs, by Shabana Khan, Manuel Alcarazo Selective C-H Activations Using Frustrated Lewis Pairs. Applications in Organic Synthesis, by Paul Knochel, Konstantin Karaghiosoff, Sophia Manolikakes FLP-Mediated Activations and Reductions of CO2 and CO, by Andrew E. Ashley, Dermot O’Hare Radical Frustrated Lewis Pairs, by Timothy H. Warren and Gerhard Erker Polymerization by Classical and Frustrated Lewis Pairs, by Eugene Y.-X. Chen Frustrated Lewis Pairs Beyond the Main Group: Transition Metal-Containing Systems, by D. Wass Reactions of Phosphine-Boranes and Related Frustrated Lewis Pairs with Transition Metal Complexes, by Abderrahmane Amgoune, Ghenwa Bouhadir, Didier Bourissou

A guide to the effective catalysts and latest advances in CO2 conversion in chemicals and fuels Carbon dioxide hydrogenation is one of the most promising and economic techniques to utilize CO2 emissions to produce value-added chemicals. With contributions from an international team of experts on the topic, CO2 Hydrogenation Catalysis offers a comprehensive review of the most recent developments in the catalytic hydrogenation of carbon dioxide to formic acid/formate, methanol, methane, and C2+ products. The book explores the electroreduction of carbon dioxide and contains an overview on hydrogen production from formic acid and methanol. With a practical review of the advances and challenges in future CO2 hydrogenation research, the book provides an important guide for researchers in academia and industry working in the field of catalysis, organometallic chemistry, green and sustainable chemistry, as well as energy conversion and storage. This important book: Offers a unique review of effective catalysts and the latest advances in CO2 conversion Explores how to utilize CO2 emissions to produce value-added chemicals and fuels such as methanol, olefins, gasoline, aromatics Includes the latest research in homogeneous and heterogeneous catalysis as well as electrocatalysis Highlights advances and challenges for future investigation Written for chemists, catalytic chemists, electrochemists, chemists in industry, and chemical engineers, CO2 Hydrogenation Catalysis offers a comprehensive resource to understanding how CO2 emissions can create value-added chemicals.

In this comprehensive book, one of the leading experts, Shun-Ichi Murahashi, presents all the important facets of modern synthetic chemistry using Ruthenium, ranging from hydrogenation to metathesis. In 14 contributions, written by an international authorship, readers will find all the information they need about this fascinating and extraordinary chemistry. The result is a high quality information source and a indispensable reading for everyone working in organometallic chemistry. From the contents: Introduction (S.-I. Murahashi) Hydrogenation and Transfer Hydrogenation (M. Kitamura and R. Noyori) Oxidations (S.-I. Murahashi and N. Komiya) Carbon-Carbon Bond Formations via Ruthenacycle Intermediates (K. Itoh) Carbon-Carbon Bond Formation via pi-Allylruthenium Intermediates (T. Mitsudo) Olefin Metathesis (R. H. Grubbs) Cyclopropanation (H. Nishiyama) Nucleophilic Addition to Alkynes and Reactions via Vinylidene Intermediates (P. Dixneuf) Reactions via C-H Activation (N. Chatani) Lewis Acid Reactions (E. P. Kundig) Reactions with CO and CO2 (T. Mitsudo) Isomerization of Organic Substrates Catalyzed by Ruthenium Complexes (H. Suzuki) Radical Reactions (H. Nagashima) Bond Cleavage Reactions (S. Komiya)

Homogeneous hydrogenation is one of the most thoroughly studied fields of homogeneous catalysis. The results of these studies have proved to be most important for an understanding of the underlying principles of the activation of small molecules by transition metal complexes. During the past three decades homogeneous hydrogenation has found widespread application in organic chemistry, including the production of important pharmaceuticals, especially where a sophisticated degree of selectivity is required. This volume presents a general account of the main principles and applications of homogeneous hydrogenation by transition metal complexes. Special attention is devoted to the mechanisms by which these processes occur, and the role of the recently discovered complexes of molecular hydrogen is described. Sources of hydrogen, other than H2, are also considered (transfer hydrogenation). The latest achievements in highly stereoselective hydrogenations have made possible many new applications in organic synthesis. These applications are documented by giving details of the reduction of important unsaturated substrates (alkenes, alkynes, aldehydes and ketones, nitrocompounds, etc.). Hydrogenation in biphasic and phase transfer catalyzed systems is also described. Finally, a discussion of the biochemical routes of H2 activation highlights the similarities and differences in performing hydrogenation in both natural and synthetic systems. For researchers working in the fields of homogeneous catalysis, especially in areas such as pharmaceuticals, plastics and fine chemicals.

A guide and comprehensive review of the most recent advances in homogeneous hydrogenation with non-precious catalysts In recent years a great deal of research has been applied to homogeneous hydrogenation with non-precious catalysis. Homogeneous Hydrogenation with Non-Precious Catalysts offers a review of the latest developments and advances in the field. In addition, the book explores the transition metal catalysis and the concept of frustrated-lewis-pair (FLP) and enzymatic processes. The editor?a noted expert on the topic?discusses the various catalysts and puts the focus on the synthetic vantage point, highlighting the functional group transformation enabled by the respective catalyst. Homogeneous Hydrogenation with Non-Precious Catalysts also presents the industrial view of the topic and includes an overview of the various catalysts by functional group transformations. This important book: -Offers a comprehensive presentation of the newest development in this emerging field -Highlights the transition metal catalysis, the frustrated-lewis-pair (FLP) concept, and enzymatic processes -Provides an industrial perspective of the topic -Includes an overview of the various catalysis by functional group transformations Written for organic chemists, researchers in synthetic chemistry, and industry professionals, Homogeneous Hydrogenation with Non-Precious Catalysts offers a comprehensive and accessible guide to the most recent advances in the field. [/COPY_WEB_CATALOG]

The series Topics in Current Chemistry Collections presents critical reviews from the journal Topics in Current Chemistry organized in topical volumes. The scope of coverage is all areas of chemical science including the interfaces with related disciplines such as biology, medicine and materials science. The goal of each thematic volume is to give the non-specialist reader, whether in academia or industry, a comprehensive insight into an area where new research is emerging which is of interest to a larger scientific audience. Each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years are presented using selected examples to illustrate the principles discussed. The coverage is not intended to be an exhaustive summary of the field or include large quantities of data, but should rather be conceptual, concentrating on the methodological thinking that will allow the non-specialist reader to understand the information presented. Contributions also offer an outlook on potential future developments in the field.

The collection of contributions in this volume presents the most up-to-date findings in catalytic hydrogenation. The individual chapters have been written by 36 top specialists each of whom has achieved a remarkable depth of coverage when dealing with his particular topic. In addition to detailed treatment of the most recent problems connected with catalytic hydrogenations, the book also contains a number of previously unpublished results obtained either by the authors themselves or within the organizations to which they are affiliated.Because of its topical and original character, the book provides a wealth of information which will be invaluable not only to researchers and technicians dealing with hydrogenation, but also to all those concerned with homogeneous and heterogeneous catalysis, organic technology, petrochemistry and chemical engineering.