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N-Heterocyclic Carbenes in Transition Metal Catalysis and Organocatalysis

Author : Catherine S.J. Cazin
Publisher : Springer Science & Business Media
Page : 348 pages
File Size : 34,43 MB
Release : 2010-10-04
Category : Science
ISBN : 9048128668

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N-Heterocyclic Carbenes in Transition Metal Catalysis and Organocatalysis features all catalytic reactions enabled by N-heterocyclic carbenes (NHCs), either directly as organocatalysts or as ligands for transition metal catalysts. An explosion in the use of NHCs has been reported in the literature during the past seven years making this comprehensive overview highly apropos. The book begins with an introductory overview of NHCs which could have been subtitled all you need to know about NHCs. The main body of the book is dedicated to applications of NHCs in catalysis. In addition to the success stories of NHCs in metathesis, NHCs in cross coupling and more recently NHCs in organocatalysis, all other less publicized areas are also covered. As the success of NHCs is generally attributed to their potential to stabilize metal centres, the inclusion of a chapter on the decomposition of NHC catalysts is pertinent. The book closes with a chapter describing the applications of NHCs in industrial processes, which is the first coverage of its kind, and brings a unique industrial context to this book. Included in this book: Historical aspects of NHCs Synthetic pathways to NHC precursors, free NHCs and complexes Methods of characterisation of NHCs and related complexes Electronic properties of NHCs Steric properties of NHCs and models for their description NHCs for metathesis and cross-coupling reactions NHCs as organocatalysts NHC Transition-Metal mediated oxidations, additions to multiple bonds, polymerisation and oligomerisation, cyclisations, direct arylations, reactions involving CO, C-F and C-H bond activation, ... Decomposition of NHC-containing catalysts Industrial applications involving NHC-containing catalysts N-Heterocyclic Carbenes in Transition Metal Catalysis and Organocatalysis provides a fresh view of NHCs since most contributors are young emerging researchers in the field of homogeneous catalysis using NHCs. This group of contributors is complemented by highly established academic researchers and an industrialist. This book is comprehensive, from the basic features of NHCs to the latest advances, hence it is suitable for both the novice and the expert.

Transition Metal Complexes of N-heterocyclic Carbenes and Derivatives Thereof

Author : Timothy Gordon Larocque
Publisher :
Page : pages
File Size : 38,78 MB
Release : 2013
Category :
ISBN :

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N-heterocyclic carbenes (NHCs) have played a dominant role in organometallic chemistry for decades and revolutionized the field of homogenous catalysis. NHCs have been thoroughly studied, both experimentally and theoretically, and have shown unique reactivity towards transition metals, chalcogens, azides and pnictogens. This thesis is aimed at utilizing the unique reactivity of N-heterocyclic carbenes to develop novel, robust catalysts to mediate organic transformations. The multi-faceted work within this thesis explores the use of NHCs as ancillary ligands on early and late transition metals as potential catalysts for olefin polymerization and ring-closing metathesis, respectively. This work also includes exploring the synthesis and coordination of ancillary ligands derived from the unique reactivity of NHCs towards azides, chalcogens and pnictinidenes. The reactivity of a novel aryl-substituted acyclic imino-N-heterocyclic carbene to early transition metals, cyclooctasulfur and Grubbs-type ruthenium benzylidene complexes was explored. The reactivity of imidazol-2-imide towards Grubbs-type ruthenium benzylidene complexes and the synthesis and coordination of a novel group of ligands bearing an imidazol-2-imine scaffold were also explored. Lastly, this work will include the reactivity of IMes=PPh to Grubbs-type ruthenium benzylidene complexes.

N-Heterocyclic Carbenes in Transition Metal Catalysis

Author : Frank Glorius
Publisher : Springer
Page : 240 pages
File Size : 28,88 MB
Release : 2007-02-05
Category : Science
ISBN : 3540369309

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In this book leading experts have surveyed major areas of application of NHC metal complexes in catalysis. The authors have placed a special focus on nickel- and palladium-catalyzed reactions, on applications in metathesis reactions, on oxidation reactions and on the use of chiral NHC-based catalysts. This compilation is rounded out by an introductory chapter and a chapter dealing with synthetic routes to NHC metal complexes.

N-Heterocyclic Carbenes in Transition Metal Catalysis and Organocatalysis

Author : Catherine S.J. Cazin
Publisher : Springer
Page : 340 pages
File Size : 21,45 MB
Release : 2010-11-04
Category : Science
ISBN : 9789048128679

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N-Heterocyclic Carbenes in Transition Metal Catalysis and Organocatalysis features all catalytic reactions enabled by N-heterocyclic carbenes (NHCs), either directly as organocatalysts or as ligands for transition metal catalysts. An explosion in the use of NHCs has been reported in the literature during the past seven years making this comprehensive overview highly apropos. The book begins with an introductory overview of NHCs which could have been subtitled all you need to know about NHCs. The main body of the book is dedicated to applications of NHCs in catalysis. In addition to the success stories of NHCs in metathesis, NHCs in cross coupling and more recently NHCs in organocatalysis, all other less publicized areas are also covered. As the success of NHCs is generally attributed to their potential to stabilize metal centres, the inclusion of a chapter on the decomposition of NHC catalysts is pertinent. The book closes with a chapter describing the applications of NHCs in industrial processes, which is the first coverage of its kind, and brings a unique industrial context to this book. Included in this book: Historical aspects of NHCs Synthetic pathways to NHC precursors, free NHCs and complexes Methods of characterisation of NHCs and related complexes Electronic properties of NHCs Steric properties of NHCs and models for their description NHCs for metathesis and cross-coupling reactions NHCs as organocatalysts NHC Transition-Metal mediated oxidations, additions to multiple bonds, polymerisation and oligomerisation, cyclisations, direct arylations, reactions involving CO, C-F and C-H bond activation, ... Decomposition of NHC-containing catalysts Industrial applications involving NHC-containing catalysts N-Heterocyclic Carbenes in Transition Metal Catalysis and Organocatalysis provides a fresh view of NHCs since most contributors are young emerging researchers in the field of homogeneous catalysis using NHCs. This group of contributors is complemented by highly established academic researchers and an industrialist. This book is comprehensive, from the basic features of NHCs to the latest advances, hence it is suitable for both the novice and the expert.

N-heterocyclic Carbene Group 4 Metal Complexes

Author : Charles Romain
Publisher :
Page : 194 pages
File Size : 26,49 MB
Release : 2011
Category :
ISBN :

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The design of a novel NHC chelating ligand allowed the beneficial “association” of a soft NHC moiety with hard oxophilic group 4 metal which lead to the synthetize of a broad family of NHC group 4 metal complexes. Remarkably, the (OCO)MXX' group 4 chelates (X, X' = amido, alkoxide, chloride) were all found to be stable and robust entities with the NHC moiety truly and solely acting as an ancillary ligand under catalytic conditions. Attempts to access alkyl group 4 derivatives opened the way to an unprecedented NHC--involving alkyl/benzyl rearrangement reaction, there by constituting the first instance in which a NHC moiety coordinated to a high--oxidation--state and oxophilic transition metal NHC complex exhibited such a behavior. The prepared NHC group 4 metal alkoxide species were investigated in polymerization catalysis and found to be suitable initiators for the controlled and highly stereoselective ring--opening polymerization (ROP) of cyclic esters (lactide, a dimer of lactic acid) and cyclic carbonates (trimethylene carbonate), demonstrating the robustness of such species in catalytic conditions. These results constitute the first instance in which a NHC--based oxophilic metal catalyst is competitive and, to some extent, even performs better than current systems the area.