Author: David Armstrong
Publisher:
ISBN:
Category :
Languages : en
Pages :
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Book Description
In the first section of this thesis, the synthesis and reactivity of the first reported palladium(IV) aryldiazenido complex is explored, as well as its relevance toward the potential for catalytic coupling cycles based on the Pd(II)/Pd(IV) redox pair. The synthesis was achieved by two-electron oxidation of the anionic palladium(II) complex KPd(Tp*)Me2 (Tp*- = hydridotris(3,5-dimethylpyrazolyl)borate) by an aryldiazonium cation. The resulting Pd(IV) complex could be cleanly isolated in good yields, is stable for weeks as a solid when kept cold, and decays in solution over a period of days at room temperature. The decomposition was studied in great depth by both NMR and EPR spectroscopy and it was determined that one-electron pathways were involved. From the synthesis of the Pd(IV) aryldiazenido complex, side reactions were observed whereby free Tp*- ligand could be modified via hydride abstraction by an aryldiazonium cation to form the elusive tris(pyrazolyl)borane which could be trapped and isolated as its acetone adduct in a Frustrated Lewis-pair type reaction. The resulting compound can act as a bidentate N-donor ligand with unusual axial steric bulk. Addition of a second equivalent of aryldiazonium cation further abstracts a 3,5-dimethylpyrazolide group to form a cationic intermediate which can again be trapped by acetone to form a C2-chiral cation. In the later chapters of this thesis, extensive work towards the synthesis of 1- and 2- adamantyl anion equivalents was explored, as well as their utility in the synthesis of transition metal adamantyl complexes. The development of new reliable synthetic methods to produce adamantyl magnesium and zinc compounds (including the unknown diadamantylzincs) was achieved, producing clean and shelf stable compounds. The applications of these adamantyl anions toward organometallic chemistry was investigated. It was observed that the diadamantylzinc compounds were particularly potent in transmetallation reactions, cleanly producing several new transition metal and main group adamantyl complexes. While compounds containing mercury, gold, bismuth, tungsten, and platinum have now been synthesized, those of particular interest have the potential for C-H bond activation chemistry and could open access to new compound classes of facially trifunctionalized adamantanes.
Author: Roderick Bates
Publisher: John Wiley & Sons
ISBN: 1118313666
Category : Science
Languages : en
Pages : 5
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Book Description
Transition metals open up new opportunities for synthesis, because their means of bonding and their reaction mechanisms differ from those of the elements of the s and p blocks. In the last two decades the subject has mushroomed - established reactions are seeing both technical improvements and increasing numbers of applications, and new reactions are being developed. The practicality of the subject is demonstrated by the large number of publications coming from the process development laboratories of pharmaceutical companies, and its importance is underlined by the fact that three Nobel prizes have been awarded for discoveries in this field in the 21st Century already. Organic Synthesis Using Transition Metals, 2nd Edition considers the ways in which transition metals, as catalysts and reagents, can be used in organic synthesis, both for pharmaceutical compounds and for natural products. It concentrates on the bond-forming reactions that set transition metal chemistry apart from "classical" organic chemistry. Each chapter is extensively referenced and provides a convenient point of entry to the research literature. Topics covered include: introduction to transition metals in organic synthesis coupling reactions C-H activation carbonylative coupling reactions alkene and alkyne insertion reactions electrophilic alkene and alkyne complexes reactions of alkyne complexes carbene complexes h3- or p-allyl -allyl complexes diene, dienyl and arene complexes cycloaddition and cycloisomerisation reactions For this second edition the text has been extensively revised and expanded to reflect the significant improvements and advances in the field since the first edition, as well as the large number of new transition metal-catalysed processes that have come to prominence in the last 10 years – for example the extraordinary progress in coupling reactions using “designer” ligands, catalysis using gold complexes, new opportunities arising from metathesis chemistry, and C-H activation – without neglecting the well established chemistry of metals such as palladium. Organic Synthesis Using Transition Metals, 2nd Edition will find a place on the bookshelves of advanced undergraduates and postgraduates working in organic synthesis, catalysis, medicinal chemistry and drug discovery. It is also useful for practising researchers who want to refresh and enhance their knowledge of the field.
Author: Robert H. Crabtree
Publisher: John Wiley & Sons
ISBN: 1118210859
Category : Science
Languages : en
Pages : 418
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Book Description
"One impressive and compressive book. . . . This review would have to be book size to do full justice to all the insights in this volume." —Journal of Metals Online Fully updated and expanded to reflect recent advances, this Fifth Edition of the classic text provides students and professional chemists with a comprehensive introduction to the principles and general properties of organometallic compounds, as well as including practical information on reaction mechanisms and detailed descriptions of contemporary applications. With increased focus on organic synthesis applications, nanoparticle science, and green chemistry, the Fifth Edition brings this vital resource up to date. New to the Fifth Edition: Chapters have been updated with relevant examples in the field, modern trends, and new applications; the organic applications chapter has been completely rewritten New end-of-chapter problems, along with their solutions Coverage enhanced with developments in nanoparticle science Increased focus on green chemistry An unparalleled pedagogic resource as well as a valuable working reference for professional chemists, with comprehensive coverage and up-to-date information, students and researchers in organic and organometallic chemistry will turn to The Organometallic Chemistry of the Transition Metals, Fifth Edition for the critical information they need on organometallic compounds, their preparation, and their use in synthesis.
Author: Ewa Broclawik
Publisher: Springer
ISBN: 3030117146
Category : Science
Languages : en
Pages : 540
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Book Description
This book focuses on the electronic properties of transition metals in coordination environments. These properties are responsible for the unique and intricate activity of transition metal sites in bio- and inorganic catalysis, but also pose challenges for both theoretical and experimental studies. Written by an international group of recognized experts, the book reviews recent advances in computational modeling and discusses their interplay using experiments. It covers a broad range of topics, including advanced computational methods for transition metal systems; spectroscopic, electrochemical and catalytic properties of transition metals in coordination environments; metalloenzymes and biomimetic compounds; and spin-related phenomena. As such, the book offers an invaluable resource for all researchers and postgraduate students interested in both fundamental and application-oriented research in the field of transition metal systems.
Author:
Publisher: Elsevier
ISBN: 0443294232
Category : Science
Languages : en
Pages : 298
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Book Description
Advances in Organometallic Chemistry, Volume 82, the latest release in this longstanding serial, is known for its comprehensive coverage of topics in organometallic synthesis, reactions, mechanisms, homogeneous catalysis, and more. Chapters in this new release include Pd-catalysis: a useful tool in the field of polymer synthesis. Recent advances and applications, Modern Mechanistic Approaches for the Depolymerization of Commodity Plastics via Homogeneous Metal Catalysis, Functionalization of fullerenes by transition metal catalyzed cyclization reactions, and Synergistic Metal-Ligand Reactivity in Half-Sandwich Complexes of Fe, Co, and Ni for Bond Activation and Catalysis. - Contains contributions from leading authorities in the field of organometallic chemistry - Covers topics in organometallic synthesis, reactions, mechanisms, homogeneous catalysis, and more - Informs and updates readers on the latest developments in the field - Carefully edited to provide easy-to-read material
Author: Ray Hoff
Publisher: John Wiley & Sons
ISBN: 0470504420
Category : Technology & Engineering
Languages : en
Pages : 599
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Book Description
A one-stop resource for understanding and applying polymerization catalysts An edited volume featuring contributions from leading researchers, the Handbook of Transition Metal Polymerization Catalysts covers the design and synthesis of catalysts, and their applications in synthesis of polymers. Dealing with those polymerization catalysts that afford commercially acceptable yields of polymer with respect to catalyst mass and promising newer catalysts, this practical reference provides polymer and organic chemists with a comprehensive overview of the known methods for developing and applying these important catalysts. With both recent advances and historically important catalysts, the subjects covered in this text include: Metal alkyls and other compounds that function as co-catalysts with a large number of catalysts The varieties of porous silica either necessary or valuable in certain catalyst formulations Catalyst scale-up and commercialization Copper catalysts for olefin polymerization Morphology control Along with the above topics, the Handbook of Transition Metal Polymerization Catalysts provides tables of valuable data to assist in reproducing a synthesis or applying the knowledge to a new problem. Polymerization reactivities, polymer properties, monomer and solvent purity requirements, molecular weights, distribution, and reactivity ratios are also covered. The Handbook of Transition Metal Polymerization Catalysts offers an excellent one-stop resource for understanding and applying polymerization catalysts.
Author: Jesse M. Jefferis
Publisher:
ISBN:
Category :
Languages : en
Pages : 232
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Book Description
Author: Yury Kissin
Publisher: Elsevier
ISBN: 0080557996
Category : Technology & Engineering
Languages : en
Pages : 607
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Book Description
During the past 30 years, the field of alkene polymerization over transition metal catalysts underwent several major changes:1. The list of commercial heterogeneous Ziegler-Natta catalysts for the synthesis of polyethylene and stereoregular polyolefins was completely renewed affording an unprecedented degree of control over the polymer structure.2. Research devoted to metallocene and other soluble transition-metal catalysis has vastly expanded and has shifted toward complexes of transition metals with multidentate ligands.3. Recent developments in gel permeation chromatography, temperature-rising fractionation, and crystallization fractionation provided the first reliable information about differences between various active centers in transition-metal catalysts.4. A rapid development of high-resolution 13C NMR spectroscopy resulted in greatly expanded understanding of the chemical and steric features of polyolefins and alkene copolymers. These developments require a new review of all aspects of alkene polymerization reactions with transition-metal catalysts. The first chapter in the book is an introductory text for researchers who are entering the field. It describes the basic principles of polymerization reactions with transition-metal catalysts, the types of catalysts, and commercially manufactured polyolefins. The next chapter addresses the principal issue of alkene polymerization catalysis: the existence of catalyst systems with single and multiple types of active centers. The subsequent chapters are devoted to chemistry and stereochemistry of elemental reaction steps, structures of catalyst precursors and reactions leading to the formation of active centers, kinetics of polymerization reactions, and their mechanisms.The book describes the latest commercial polymerization catalysts for the synthesis of polyethylenes and polypropylene The book provides a detailed description of the multi-center nature of commercial Ziegler-Natta catalysts. The book devotes specialized chapters to the most important aspects of transition metal polymerization catalysts: the reactions leading to the formation of active centers, the chemistry and stereochemistry of elemental polymerization steps, reaction kinetics, and the polymerization mechanism. The book contains an introductory chapter for researchers who are entering the field of polymerization catalysis. It describes the basic principles of polymerization reactions with transition-metal catalysts and the types of commercially manufactured polyolefins and copolymersThe book contains over 2000 references, the most recent up to end of 2006.
Author: Florian P. Pruchnik
Publisher: Springer Science & Business Media
ISBN: 1489920765
Category : Science
Languages : en
Pages : 767
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Book Description
Organometallic chemistry belongs to the most rapidly developing area of chemistry today. This is due to the fact that research dealing with the structure of compounds and chemical bonding has been greatly intensified in recent years. Additionally, organometallic compounds have been widely utilized in catalysis, organic synthesis, electronics, etc. This book is based on my lectures concerning basic organometallic chemistry for fourth and fifth year chemistry students and on my lectures concerning advanced organometallic chemistry and homogeneous catalysis for Ph.D. graduate students. Many recent developments in the area of organometallic chemistry as weIl as homogeneous catalysis are presented. Essential research results dealing with a given class of organometallic compounds are discussed briefly. Results of physicochemical research methods of various organometallic compounds as weIl as their synthesis, properties, structures, reactivities, and applications are discussed more thoroughly. The selection of tabulated data is arbitrary because, often, it has been impossible to avoid omissions. Nevertheless, these data can be very helpful in understanding properties of organometaIlic compounds and their reactivities. All physical data are given in SI units; the interatomic distances are given in pm units in figures and tables. I am indebted to Professor S. A. Duraj for translating and editing this book. His remarks, discussions, and suggestions are greatly appreciated. I also express gratitude to Virginia E. Duraj for editing and proofreading.
Author: Isaac B. Bersuker
Publisher: John Wiley & Sons
ISBN: 0470920858
Category : Science
Languages : en
Pages : 658
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Book Description
With more than 40% new and revised materials, this second edition offers researchers and students in the field a comprehensive understanding of fundamental molecular properties amidst cutting-edge applications. Including ~70 Example-Boxes and summary notes, questions, exercises, problem sets, and illustrations in each chapter, this publication is also suitable for use as a textbook for advanced undergraduate and graduate students. Novel material is introduced in description of multi-orbital chemical bonding, spectroscopic and magnetic properties, methods of electronic structure calculation, and quantum-classical modeling for organometallic and metallobiochemical systems. This is an excellent reference for chemists, researchers and teachers, and advanced undergraduate and graduate students in inorganic, coordination, and organometallic chemistry.
