Author: Dmitry V. Gutsulyak
Publisher:
ISBN:
Category :
Languages : en
Pages :

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Author: Van Hung Mai
Publisher:
ISBN:
Category :
Languages : en
Pages :

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This thesis presents the preparation and catalytic reactivity of novel half-sandwich ruthenium complexes supported by N-Heterocyclic Carbene (NHC) ligands. The cationic half-sandwich ruthenium complexes [Cp(IPr)Ru(CH3CN)2]+ show interesting reactivities toward the transfer hydrogenation of different unsaturated substrates, such as ketones, olefins, N-heterocycles, and nitriles. Kinetic studies disclose that a neutral trishydride ruthenium complex is actually involved in the catalytic cycle, playing the role as a resting state. Further investigations on the sub-class of trishydride ruthenium complexes bearing NHC ligands (Cp'(NHC)RuH3) reveal that these complexes have an unusual and great catalytic performance toward the hydrodefluorination (HDF) of fluorinated aromatic and aliphatic compounds. The combined kinetic studies, cross-over experiments and rate law analysis suggest an unusual mechanistic pathway for the Cp*(IPr)RuH3 catalyzed HDF. This study is one of the rare examples where isopropanol is employed as a reducing agent for the metal-mediated HDF reaction. A class of silyl dihydride ruthenium complexes, derived from Cp(IPr)RuH3 are prepared. These silyl hydrido derivatives are great compounds for the study of the inter ligand hypervalent interaction (IHI), an interesting phenomenon for many non-classical silane complexes. This study also suggests that the replacement of phosphines by their isolobally analogous NHC ligands result in stronger IHI interactions in the corresponding compounds. Another type of non-classical interaction was systematically scrutinized in a ii series of new cationic and neutral silane sigma complexes of ruthenium bearing different silyl moieties. These new NHC-supported ruthenium complexes allow for direct comparation with the known phosphine analogues, which reveals interplay of steric and electronic factors on the extent of Si-H complexation to metal and the extent of additional interligand interactions between Ru-Cl and chlorosilane ligand. Finally, new trishydride ruthenium complexes bearing NHC ligands (Cp'(NHC)RuH3) catalyze the H/D exchange reaction of various N-heterocycle substrates; their catalytic performance can be considered as one of the mildest, and most efficient approaches.

Author: Rocco Angelo Paciello
Publisher:
ISBN:
Category :
Languages : en
Pages : 276

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Author: Woei-Min Tsai
Publisher:
ISBN:
Category : Organometallic compounds
Languages : en
Pages : 202

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Author: E W Abel
Publisher: Royal Society of Chemistry
ISBN: 1847554148
Category : Science
Languages : en
Pages : 476

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Organometallic chemistry is an interdisciplinary science which continues to grow at a rapid pace. Although there is continued interest in synthetic and structural studies the last decade has seen a growing interest in the potential of organometallic chemistry to provide answers to problems in catalysis synthetic organic chemistry and also in the development of new materials. This Specialist Periodical Report aims to reflect these current interests reviewing progress in theoretical organometallic chemistry, main group chemistry, the lanthanides and all aspects of transition metal chemistry. Specialist Periodical Reports provide systematic and detailed review coverage of progress in the major areas of chemical research. Written by experts in their specialist fields the series creates a unique service for the active research chemist, supplying regular critical in-depth accounts of progress in particular areas of chemistry. For over 80 years the Royal Society of Chemistry and its predecessor, the Chemical Society, have been publishing reports charting developments in chemistry, which originally took the form of Annual Reports. However, by 1967 the whole spectrum of chemistry could no longer be contained within one volume and the series Specialist Periodical Reports was born. The Annual Reports themselves still existed but were divided into two, and subsequently three, volumes covering Inorganic, Organic and Physical Chemistry. For more general coverage of the highlights in chemistry they remain a 'must'. Since that time the SPR series has altered according to the fluctuating degree of activity in various fields of chemistry. Some titles have remained unchanged, while others have altered their emphasis along with their titles; some have been combined under a new name whereas others have had to be discontinued. The current list of Specialist Periodical Reports can be seen on the inside flap of this volume.

Author: Manfred Bochmann
Publisher: Oxford University Press, USA
ISBN: 0199668213
Category : Science
Languages : en
Pages : 429

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A succinct review of the essential concepts of organometallic chemistry, enriched throughout with examples that demonstrate how our understanding of organometallic chemistry has led to new applications in research and industry - not least in relation to catalysis.

Author:
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Category :
Languages : en
Pages :

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Author: Sun Hwa Lee
Publisher:
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Category :
Languages : en
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Author: Y.Z. Voloshin
Publisher: Elsevier
ISBN: 0080529178
Category : Science
Languages : en
Pages : 433

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Clathrochelates are compounds which contain a metal ion encapsulated within a three dimensional cage of macrobicyclic ligand atoms. Within this cage the metal has unique properties and is to a great extent isolated from environmental factors. Such complexes are suitable as models of the most essential biological systems, membrane transport, electron carriers, highly selective and sensitive analytical reagents, catalysts for photochemical and redox processes, cation and anion receptors, etc. The aim of this monograph is to generalize and analyze experimental and theoretical data on clathrochelates in order to promote further research in this promising field of chemistry.Chapter 1 gives general concepts of complexes with encapsulated metal ions, discusses basic specific features of these compounds, considers and characterizes the main types of compounds with encapsulated metal ions and the main classes of clathrochelates, and includes the current nomenclature. Chapter 2 deals with the pathways of clathrochelate synthesis and the general procedures for the synthesis of macrobicyclic tris-dioximates, phosphorus-containing tris-diiminates, sepulchrates, sarcophagi-nates, and polyene and other types of clathrochelate complexes. Chapter 3 concerns studies of the electronic and spatial structure of clathrochelate complexes. In Chapter 4, the kinetics and mechanism of synthesis and decomposition reactions of macrobicyclic tris-dioximates, sarcophaginates, and sepulchrates in solution and gas phases are discussed. Chapter 5 considers the electrochemical, photochemical, and some other characteristics of clathrochelates and their applications associated with these characteristics. Finally, the practical applications of the unique properties of clathrochelates and perspectives on the synthesis of new clathrochelates are described in Chapters 6 and 7, respectively.

Author: Robert H. Crabtree
Publisher:
ISBN:
Category : Chimie organométallique
Languages : en
Pages : 232

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Volume 1 reviews the preparations, properties, structure, bonding and applications of organometallic compounds of Alkali metal, Alkaline earth, Copper, Silver, Zinc, Mercury and Cadmium. It provides a clear and comprehensive overview of developments since 1993 and attempts to predict trends in the field over the next ten years. Like its predecessors, COMC (1982) and COMC-II (1995), this new work is the essential reference text for any chemist or technologist who needs to use or apply organometallic compounds. * valuable content available May 2009 as an individual volume * separate volumes will appeal to a wider chemistry and materials science audience * priced for individual researcher as well as library purchase