Synthesis, Characterization, and Reactivity of Manganese(II) Complexes Containing N-heterocyclic Carbene Ligands

Synthesis, Characterization, and Reactivity of Manganese(II) Complexes Containing N-heterocyclic Carbene Ligands
Author: Venkateswaran Mahesh Krishnan
Publisher:
Total Pages: 74
Release: 2013
Genre:
ISBN:

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A series of divalent manganese complexes containing N -heterocyclic carbene (NHC) ligands were synthesized and characterized in solution and the solid state. Chlorido complexes of Mn(II) containing the NHC ligands 1,3-dimesitylimidazol-2-ylidene (IMes) and 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) were prepared in straightforward fashion by direct carbene addition to MnCl 2 (thf)1.5. The chlorido complexes were found to be ineffective precatalysts in Kumada-type coupling reactions of simple aryl halides. Cyclic voltammetry studies of one of the chloride complexes, [MnCl2 (IMes)2 ], demonstrate no electrochemically accessible reduction events in tetrahydrofuran, possibly accounting for the lack of catalytic activity. Chlorido complexes containing both IMes and IPr ligands serve as precursors to alkyl and aryl compounds of Mn(II). Characterization of the alkyl and aryl complexes is reported, and comparisons are made between these complexes and similar compounds in the chemical literature.

Synthesis and Reactivity of Metal Complexes Containing Functionalized N-heterocyclic Carbene Ligands for Catalytic Applications

Synthesis and Reactivity of Metal Complexes Containing Functionalized N-heterocyclic Carbene Ligands for Catalytic Applications
Author: Pengfei Ai
Publisher:
Total Pages: 0
Release: 2015
Genre:
ISBN:

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The purpose of this work was the synthesis of N,N'-diphosphanyl-functionalized NHC ligands andtheir coordination chemistry. The novel stable and rigid tridentate N,N'-diphosphanyl-imidazol-2-ylidene was synthesized and experimental and computational information on its stability weregained. It served as a unique platform for the synthesis of novel mono-, di-, tri-, penta-, hexanuclear complexes with the coinage metals (Cu, Ag and Au), exhibiting rare structural features. The mono- and dinuclear complexes with one or two dangling P-donors provided rational access to heterotrinuclear complexes. All these coinage metal complexes have short metal-metalseparations, indicating the presence of d10-d10 interactions, and display excellent luminescentproperties. Partial or complete transmetallation of the homotrinuclear Cu or Ag complexes withPd(0) precursors led to hetero-trinuclear complexes with d10-d10 interactions. In addition to itsbridging behavior, this ligand also showed its chelating behavior in Pd or Cr(III) complexes. Thelatter displayed superior performance in ethylene oligomerization than the Cr(II) complexes andgave mostly oligomers.

The Organometallic Chemistry of N-heterocyclic Carbenes

The Organometallic Chemistry of N-heterocyclic Carbenes
Author: Han Vinh Huynh
Publisher: John Wiley & Sons
Total Pages: 352
Release: 2017-02-03
Genre: Science
ISBN: 1118698797

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The Organometallic Chemistry of N-heterocyclic Carbenes describes various aspects of N-heterocyclic Carbenes (NHCs) and their transition metal complexes at an entry level suitable for advanced undergraduate students and above. The book starts with a historical overview on the quest for carbenes and their complexes. Subsequently, unique properties, reactivities and nomenclature of the four classical NHCs derived from imidazoline, imidazole, benzimidazole and 1,2,4-triazole are elaborated. General and historically relevant synthetic aspects for NHCs, their precursors and complexes are then explained. The book continues with coverage on the preparation and characteristics of selected NHC complexes containing the most common metals in this area, i.e. Ni, Pd, Pt, Ag, Cu, Au, Ru, Rh and Ir. The book concludes with an overview and outlook on the development of various non-classical NHCs beyond the four classical types. Topics covered include: Stabilization, dimerization and decomposition of NHCs Stereoelectronic properties of NHCs and their evaluation Diversity of NHCs Isomers of NHC complexes and their identification NMR spectroscopic signatures of NHC complexes normal, abnormal and mesoionic NHCs The Organometallic Chemistry of N-heterocyclic Carbenes is an essential resource for all students and researchers interested in this increasingly important and popular field of research.

N-Heterocyclic Carbenes

N-Heterocyclic Carbenes
Author: Steven P. Nolan
Publisher: John Wiley & Sons
Total Pages: 690
Release: 2014-07-07
Genre: Science
ISBN: 3527671242

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This comprehensive reference and handbook covers in depth all major aspects of the use of N-heterocyclic carbene-complexes in organic synthesis: from the theoretical background to characterization, and from cross-coupling reactions to olefin metathesis. Edited by a leader and experienced scientist in the field of homogeneous catalysis and use of NHCs, this is an essential tool for every academic and industrial synthetic chemist.

N-Heterocyclic Carbenes in Transition Metal Catalysis and Organocatalysis

N-Heterocyclic Carbenes in Transition Metal Catalysis and Organocatalysis
Author: Catherine S.J. Cazin
Publisher: Springer Science & Business Media
Total Pages: 348
Release: 2010-10-04
Genre: 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.