Download or read book Hydroamination and Hydrosilylation Catalyzed by Cationic Palladium and Nickel allyl Complexes Supported by 3 iminophosphine Ligands written by Hosein Tafazolian and published by . This book was released on 2016 with total page 195 pages. Available in PDF, EPUB and Kindle. Book excerpt: Chapter 1. A brief introduction to organometallic chemistry and catalysis is presented to explain the basics of the field to the reader. A few examples of catalysis, mainly hydroamination and hydrosilylation, and their mechanisms are presented. The significance of ligands in catalysis is also discussed. Chapter 2. Six new 3-iminophosphine ligands and their cationic (allyl)palladium complexes were synthesized. These catalytically active palladium complexes were utilized in the hydroamination of cyclohexylallene with secondary amines in order to better understand the mechanism of this hydroamination reaction. The kinetics of the reaction were also studied with the help of time-resolved proton NMR spectroscopy, as well as deuterium labeling experiments. Chapter 3. Four new [(3-iminophosphine)nickel(allyl)]OTf complexes were synthesized and characterized by NMR spectroscopy, elemental analysis, and X-ray crystallography. Equimolar reactions of these new complexes with secondary amines provided useful information on the activation of these complexes in the presence of secondary amines. They also catalyzed the hydroamination of terminal allenes with secondary amines to produce allylamines in moderate to high yields, which were then characterized by proton and carbon NMR spectroscopy and high resolution mass spectrometry. Chapter 4. A previously synthesized [(3-iminophosphine)palladium(allyl)]OTf complex was found to be an efficient catalyst for the hydrosilylation of allenes with a wide range of hydrosilanes. Several new allyl- and vinylsilanes were synthesized catalytically and fully characterized. The observed regioselectivity and a double labeled H/D experiment resolved the mechanism of the reaction while also explaining its regioselectivity. Chapter 5. Various cationic palladium and nickel complexes were investigated in the hydrosilylation of imines, ketones, and alkynes. Several new allylamine, silylether and vinylsilane compounds were formed in this study and characterized. Substrate scope and mechanisms of the catalytic reactions are discussed.
Download or read book Hydroamination and Hydrosilylation Catalyzed by Group IV Metal Complexes written by Elena Smolensky and published by . This book was released on 2007 with total page 152 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Transition metal Complexes in Catalytic Homogeneous Hydrosilylation written by and published by . This book was released on 1978 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Various transition-metal complexes, (i) Rh(acac)3.-Et3Al;(li) Rli(acac)3; (iii) Ni(acac)2-EtiAlOEt; (iv) Co2(CO)8; (v)H2PtCl6 + co-catalyst; and (vi) Pt(acac)2 have been studied as hydrosilylation catalysts. In addition, (vii), metal vapours were examined as potential catalysts. In general, addition reactions were found, tnt surprisingly, with certain aryl olefins substitution was observed.The results have been discussed with emphasis on organic product distribution, and mechanisms are proposed.Both the Zieglcr-Natta system, (i), and lth(acac) 3 alone, (ii), have been shown to be active hydrosilylation catalysts. Generally they show similar behaviour, but with some unsaturates the systems yield slightly different products.Both the systems (i) and (ii), are active catalysts for the hydro- si .ylation of internal acetylenes via a cis- addition. However, terminal acetylenes are polymerised by the Ziegler system, (i), whilst with (ii) they react to give the trans- adduct of the type RCII-CHSiX3, again by a cis- addition:Addition to internal olefins with either catalyst system results in the formation of terminal adducts of the type RCIi2CIÎ2SiX3 (R = alkyl). However, with alkylsllanes,Rh(acac) 3-Et3Al, (i), catalyses the hydrosilylation of terminal olefins to produce a mixture of all possible isomers of the formula n-Cmii2m+is^3 (m = 6 or 8) :Rh(acac) 3-Et3AiC4H9CH=CH2+ HSiEt3 -- > n-C6H13SiEt3 + n-C4H9CH(SiEt^ CH3 60° C, 15 h+ n-C3H7CH(SiEt^CH2CH3With alkoxy- or aryl-silanes, or when Rh(acac)3, (ii), is used as catalyst, terminal olefins yield only terminal adducts. Both catalyst systems are also active catalysts for the hydrosilylation of conjugated dienes, resulting principally in 1,4- addition:CH2:CHC(CHs):CH2 + HSiEt3 --Y CH3CH: C(CH;$ CH^iE^The general similarity in product suggests that both systems follow a similar mechanism, and it is proposed that any differences in products that occur are due to either a bimetallic intermediate In the Ziegler system, or the difference in mode of reduction between the systems.Rh(acac)3, (ii), can also be used as a hydrosilylation catalyst for unsaturates containing functional groups, which normally react with the co-catalyst of the Ziegler system. However, for substituted allyl compounds reduction predominates, and no hydrosilylated adducts are observed.Ni(acac)2-Et2A10Et, (iii), is an active catalyst for the hydrosilylation of 1,3- and 1,4-cyclohexadiene resulting in the product of 1,4- addition to the conjugated system, ¿H2CH2CH2CH: CHCHSiX3.Ni(acac) 2-Et2A10Et -- V RT, 8h, HSiX3Ni(acac) 2-Et2A10Et SiX3 -4 PPh3, RT, 8h, HSiXThis system is inactive for 1,3-cyclo-octadiene, where a stable nickel-diene complex is formed, but 1,3-COD can be hydrosilylated using Co^CO)«, (iv), as catalyst. 1,3- And 1,4-cyclohexadiene are alsohydrosilylated using Co2CO)g and all result in the allyl-substituted products, ¿H2( CH2)nCH: CHbHSiX3 (n = 2 or 4). The reaction is proposed to go by a 1,4 - addition involving a rr-allyl-cobalt intermediate.Chloroplatinic acid, a known hydrosilylation catalyst, hi comet« less active in the presence of a reducing agent as co-catalyst. Pt(acac) 2 is also inactive in the presence of a reducing co-catalyst, but alone,(vi), is a moderately active hydrosilylation catalyst for acetylenes and olefins, resulting in the adducts described for chloroplatinic acid, ft is, however, only weakly active for conjugated dienes.An exploratory study of the use of metal vapours in hydrosilylation catalysis has shown that the co-condensation of transition-metal vapours with isoprene and silane at liquid nitrogen temperatures produces some catalytically active systems. Of the elements of the first transition series which were investigated, nickel was found to be very active, with high stereospecificity, 207 and cobalt and iron showed moderate activity. The product formed by these systems is that of 1,4- addition, trans- CH3CH: C(CH3) CH2SiX3, and it is proposed that this involves a TT-allyl-metal complex, and that the active catalyst is a metal(O)- isoprene complex.Although addition reactions predominated in this study, Rh(acac) 3- Et3Al, (i), and Rh(acac) 3, (ii), both catalysed a substitution reaction with styrene. In attempts to hydrosilylate styrene, the principal product, formed in 70% yield, was the substitution product trans- C6H5CH:CHSiX3 (X = Et or EtO), with only the p-adduct C6H5CH2CH2SiX3 formed in measurable amounts. Elucidation of the reaction mechanism is not complete, but a variation of product distribution observed on variation of the reducing co-catalyst witht .e Ziegler system, (i), again implies that a bimetallic intermediate is involved in the reaction.fSjiThe reactivity of the systems under study is generally comparable, at the concentrations of catalyst used (~ 1 mol %, depending on silane), to that of chloroplatinic acid, except in the case of the co-condensation of nickel vapour, where the reactivity is considerably greater. The same system is also particularly stereospecific, resulting in only one adduct. A pure isomer is also obtained in the hydrosilylation of cyclic dienes with either Ni(acac)2~Et2A10Et or Co2(CO)g as catalyst, but the remaining systems do not show such a high degree of regularity.
Download or read book Cationic Nickel and Palladium Complexes with Bidentate Ligands for the C C Linkage of Olefins written by Stefan Mecking and published by . This book was released on 2008 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Hydrosilylation written by Bogdan Marciniec and published by Springer Science & Business Media. This book was released on 2008-11-09 with total page 424 pages. Available in PDF, EPUB and Kindle. Book excerpt: For fifty years, Hydrosilylation has been one of the most fundamental and elegant methods for the laboratory and industrial synthesis of organosilicon and silicon related compounds. Despite the intensive research and continued interest generated by organosilicon compounds, no comprehensive book incorporating its various aspects has been published this century. The aim of this book is to comprehensively review the advances of hydrosilylation processes since 1990. The survey of the literature published over the last two decades enables the authors to discuss the most recent aspects of hydrosilylation advances (catalytic and synthetic) and to elucidate the reaction mechanism for the given catalyst used and the reaction utilization. New catalytic pathways under optimum conditions necessary for efficient synthesis of organosilicon compounds are presented. This monograph shows the extensive development in the application of hydrosilylation in organic and asymmetric syntheses and in polymer and material science.
Download or read book Gold Chemistry written by Fabian Mohr and published by John Wiley & Sons. This book was released on 2009-04-20 with total page 425 pages. Available in PDF, EPUB and Kindle. Book excerpt: Written by world-class authors, this most recent major book on the topic highlights new and current trends as well as future directions. It is comprehensive in its scope, covering all aspects of gold chemistry -- from homogeneous to heterogeneous catalysis, from supramolecular assemblies to sensors and medicinal applications. The result is an invaluable work for both organic and inorganic chemists working in universities and industry, as well as material scientists.
Download or read book Zeolite Microporous Solids Synthesis Structure and Reactivity written by E.G. Derouane and published by Springer Science & Business Media. This book was released on 2012-12-06 with total page 635 pages. Available in PDF, EPUB and Kindle. Book excerpt: Intensive research on zeolites, during the past thirty years, has resulted in a deep understanding of their chemistry and in a true zeolite science, including synthesis, structure, chemical and physical properties, and catalysis. These studies are the basis for the development and growth of several industrial processes applying zeolites for selective sorption, separation, and catalysis. In 1983, a NATO Advanced Study Institute was organized in Alcabideche (portugal) to establish the State-of-the-Art in Zeolite Science and Technology and to contribute to a better understanding of the structural properties of zeolites, the configurational constraints they may exert, and their effects in adsorption, diffusion, and catalysis. Since then, zeolite science has witnessed an almost exponential growth in published papers and patents, dealing with both fundamentals issues and original applications. The proposal of new procedures for zeolite synthesis, the development of novel and sophisticated physical techniques for zeolite characterization, the discovery of new zeolitic and related microporous materials, progresses in quantum chemistry and molecular modeling of zeolites, and the application of zeolites as catalysts for organic reactions have prompted increasing interest among the scientific community. An important and harmonious interaction between various domains of Physics, Chemistry, and Engineering resulted therefrom.
Download or read book Ligand Design in Metal Chemistry written by Mark Stradiotto and published by John Wiley & Sons. This book was released on 2016-09-01 with total page 448 pages. Available in PDF, EPUB and Kindle. Book excerpt: The design of ancillary ligands used to modify the structural and reactivity properties of metal complexes has evolved into a rapidly expanding sub-discipline in inorganic and organometallic chemistry. Ancillary ligand design has figured directly in the discovery of new bonding motifs and stoichiometric reactivity, as well as in the development of new catalytic protocols that have had widespread positive impact on chemical synthesis on benchtop and industrial scales. Ligand Design in Metal Chemistry presents a collection of cutting-edge contributions from leaders in the field of ligand design, encompassing a broad spectrum of ancillary ligand classes and reactivity applications. Topics covered include: Key concepts in ligand design Redox non-innocent ligands Ligands for selective alkene metathesis Ligands in cross-coupling Ligand design in polymerization Ligand design in modern lanthanide chemistry Cooperative metal-ligand reactivity P,N Ligands for enantioselective hydrogenation Spiro-cyclic ligands in asymmetric catalysis This book will be a valuable reference for academic researchers and industry practitioners working in the field of ligand design, as well as those who work in the many areas in which the impact of ancillary ligand design has proven significant, for example synthetic organic chemistry, catalysis, medicinal chemistry, polymer science and materials chemistry.
Download or read book Catalytic Asymmetric Synthesis written by Takahiko Akiyama and published by John Wiley & Sons. This book was released on 2022-05-27 with total page 798 pages. Available in PDF, EPUB and Kindle. Book excerpt: Catalytic Asymmetric Synthesis Seminal text presenting detailed accounts of the most important catalytic asymmetric reactions known today This book covers the preparation of enantiomerically pure or enriched chemical compounds by use of chiral catalyst molecules. While reviewing the most important catalytic methods for asymmetric organic synthesis, this book highlights the most important and recent developments in catalytic asymmetric synthesis. Edited by two well-qualified experts, sample topics covered in the work include: Metal catalysis, organocatalysis, photoredox catalysis, enzyme catalysis C–H bond functionalization reactions Carbon–carbon bond formation reactions, carbon–halogen bond formation reactions, hydrogenations, polymerizations, flow reactions Axially chiral compounds Retaining the best of its predecessors but now thoroughly up to date with the important and recent developments in catalytic asymmetric synthesis, the 4th edition of Catalytic Asymmetric Synthesis serves as an excellent desktop reference and text for researchers and students, from upper-level undergraduates all the way to experienced professionals in industry or academia.
Download or read book Organic Reaction Mechanisms 2015 written by A. C. Knipe and published by John Wiley & Sons. This book was released on 2019-02-08 with total page 720 pages. Available in PDF, EPUB and Kindle. Book excerpt: Organic Reaction Mechanisms 2015, the 51st annual volume in this highly successful and unique series, surveys research on organic reaction mechanisms described in the available literature dated 2015. The following classes of organic reaction mechanisms are comprehensively reviewed: Reaction of Aldehydes and Ketones and their Derivatives Reactions of Carboxylic, Phosphoric, and Sulfonic Acids and their Derivatives Oxidation and Reduction Carbenes and Nitrenes Nucleophilic Aromatic Substitution Electrophilic Aromatic Substitution Carbocations Nucleophilic Aliphatic Substitution Carbanions and Electrophilic Aliphatic Substitution Elimination Reactions Polar Addition Reactions Cycloaddition Reactions Molecular Rearrangements An experienced team of authors compile these reviews every year, so that the reader can rely on a continuing quality of selection and presentation.
Download or read book Nitroarenes written by Paul C. Howard and published by Springer Science & Business Media. This book was released on 2012-12-06 with total page 324 pages. Available in PDF, EPUB and Kindle. Book excerpt: Prior to 1979, consideration of the problem of the carcinogenicity of the aromatic amine class of chemicals took place primarily in poster sessions and symposia of annual meetings of the American Association for Cancer Research and analogous international associations. In November 1979 the first meeting concerned with the aromatic amines was held in Rockville, Haryland under primary sponsorship of the National Cancer Institute. The proceedings from this meeting were published as Monograph 58 of the Journal of the National Cancel' Institute in 1981. The second meeting in this series, the Second International Conference on N-Substituted Aryl Compounds, was held in March/April of 1982 in Hot Springs, Arkansas. The National Cancer Institute and The National Center for Toxicological Research were the primary sponsors of this meeting. The proceedings were published as Volume 49 of the journal En-vil'onmental Health Perspectives in 1983. The third meeting in this series was held in April of 1987 at the Dearborn Hyatt in Dearborn, Michigan. The principal sponsor of this meeting was the Heyer L. Pre ntis Comprehensive Cancer Center of Metropolitan Detroit. The proceedings, Carcinogenic and Mutagenic Responses to Aromatic Amines and Nitroal'enes, were published in 1987 by Elsevier Press. The fourth meeting was held in Cleveland, Ohio, on July 15-19, 1989.
Download or read book Isocyanide Chemistry written by V. Nenajdenko and published by John Wiley & Sons. This book was released on 2012-06-04 with total page 615 pages. Available in PDF, EPUB and Kindle. Book excerpt: The efficacy of isocyanide reactions in the synthesis of natural or naturallike products has resulted in a renaissance of isocyanide chemistry. Now isocyanides are widely used in different branches of organic, inorganic, coordination, combinatorial and medicinal chemistry. This invaluable reference is the only book to cover the topic in such depth, presenting all aspects of synthetic isonitrile chemistry. The highly experienced and internationally renowned editor has brought together an equally distinguished team of authors who cover multicomponent reactions, isonitriles in total synthesis, isonitriles in polymer chemistry and much more.
Download or read book Current Trends in Organic Synthesis written by Carlo Scolastico and published by Springer Science & Business Media. This book was released on 2012-12-06 with total page 367 pages. Available in PDF, EPUB and Kindle. Book excerpt: The last two decades have seen a rapid growth in the synthetic processing of both simple and complex molecules, aimed at meeting the needs of society in all aspects of life. Many efforts have been devoted to the development of new biologically active compounds, new materials with innovative properties such as bio-compatibility, new catalysts that allow highly selective transformations, and technologies that facilitate the synthetic pro cesses. This book is a compendium of recent progress in all these aspects of synthetic chemistry. It collects the lectures of the XII International Conference on Organic Synthesis, held in Venice from June 28 to July 2, 1998, in which the present state of art of this discipline has been reported. The topics covered include: combinatorial chemistry, new synthetic methods, stereo selective synthesis, metal-mediated synthesis, and target oriented synthesis. The book collects the contributions, in the mentioned topics, of 43 scientists from 19 different countries. The contributions presented in the Conference as plenary lectures are reported in the first section of the book. Particular attention has been dedicated to combinatorial chemistry, a new and promising methodology for the synthesis of libraries of pharmaco logically interesting compounds in order to allow the automatic pharmacological screening of thousands of compounds. The Conference has dedicated to combinatorial chemistry a mini-symposium in which scientists from academy and companies have described the current trends of this very new technology.
Download or read book Olefin Polymerization written by Walter Kaminsky and published by Wiley-VCH. This book was released on 2006-08-18 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: With an enormous velocity, olefin polymerization has expanded to one of the most significant fields in polymers since the first industrial use about 50 years ago. In 2005, 100 million tons of polyolefins were produced - the biggest part was catalyzed by metallorganic compounds. The Hamburg Macromolecular Symposium 2005 with the title "Olefin Polymerization" involved topics such as new catalysts and cocatalysts, kinetics, mechanism and polymer reaction engineering, synthesis of special polymers, and characterization of polyolefins. The conference combined scientists from different disciplines to discuss latest research results of polymers and to offer each other the possibility of cooperation. This is reflected in this volume, which contains invited lectures and selected posters presented at the symposium.
Download or read book Catalyzed Carbon Heteroatom Bond Formation written by Andrei K. Yudin and published by John Wiley & Sons. This book was released on 2010-12-01 with total page 541 pages. Available in PDF, EPUB and Kindle. Book excerpt: Written by an experienced editor widely acclaimed within the scientific community, this book covers everything fromo9xygen to nitrogen functionalities. From the contents: Palladium-Catalyzed Syntheses of Five-Member Saturated Heterocyclic and of Aromatic Heterodynes Palladium-Catalysis for Oxidative 1, 2-Difunctionalization of Alkenes Rhodium-Catalyzed Amination of C-H-Bonds Carbon-Heteroatom Bond Formation by RH(I)-Catalyzed Ring-Opening Reactions Transition Metal-Catalyzed Synthesis of Lactones and of Monocyclic and Fused Five-Membered Aromatic heterocycles the Formation of Carbon-Sulfur and Carbon-Selenium bonds by Substitution and Addition reactions catalyzed by Transition Metal Complexes New Reactions of Copper Acetylides Gold Catalyzed Addition of Nitrogen, Sulfur and Oxygen Nucleophiles to C-C Multiple Bonds. The result is an indispensable source of information for the Strategic Planning of the Synthetic routes for organic, catalytic and medicinal chemists, as well as chemists in industry.
Download or read book Applied Homogeneous Catalysis with Organometallic Compounds written by Boy Cornils and published by John Wiley & Sons. This book was released on 2017-12-26 with total page 1778 pages. Available in PDF, EPUB and Kindle. Book excerpt: The completely revised third edition of this four-volume classic is fully updated and now includes such topics as as CH-activation and multicomponent reactions. It describes the most important reaction types, new methods and recent developments in catalysis. The internationally renowned editors and a plethora of international authors (including Nobel laureate R. Noyori) guarantee high quality content throughout the book. A "must read" for everyone in academia and industry working in this field.
Download or read book Solvomercuration Demercuration Reactions in Organic Synthesis written by R.C. Larock and published by Springer Science & Business Media. This book was released on 2012-12-06 with total page 619 pages. Available in PDF, EPUB and Kindle. Book excerpt:
