Early Transition Metal Complexes of Carbene Donors Linked to Cyclopentadienyl Ring Analogues Or Amidine

Early Transition Metal Complexes of Carbene Donors Linked to Cyclopentadienyl Ring Analogues Or Amidine
Author: Susan Conde Guadano
Publisher:
Total Pages:
Release: 2010
Genre:
ISBN:

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The new indenyl-functionalised NHC potassium salt, 1-[3-(4,7-dimethylindenylpropyl)]-3- (2,6-diisopropylphenyl)imidazol-2-ylidenepotassium, has been synthesised. Complexes of titanium, zirconium and chromium containing this ligand and the two carbon bridge analogue, 1-[2-(4,7-dimethylindenyl)ethyl]-3-(2,6-diisopropylphenyl)imidazol-2 ylidene potassium, have been synthesised and characterised by X-ray crystallographic techniques. The following complexes were tested as catalysts for the oligomerisation of ethylene in the presence of MAO: 3-(2,6-diisopropylphenyl)-1-[2-(4,7-dimethylindenyl)ethyl]-imidazol-2-ylidene(tertbutylimido) titanium chloride, 3-(2,6-diisopropylphenyl)-1-[3-(4,7- dimethylindenyl)propyl]imidazol-2-ylidene(tert-butylimido)titanium chloride, 3-(2,6- diisopropylphenyl)-1-[3-(4,7-dimethylindenyl)propyl]imidazol-2-ylidenezirconium trichloride, 3-(2,6-diisopropylphenyl)-1-[2-(4,7-dimethylindenyl)ethyl]imidazol-2- ylidenezirconium trichloride, 3-(2,6-Diisopropylphenyl)-1-[2-(4,7-dimethylindenyl)ethyl]- imidazol-2-ylidenechromium dichloride, 3-(2,6-diisopropylphenyl)-1-[3-(4,7- (dimethylindenyl))propyl]imidazol-2-ylidene chromium dichloride, 3-(2,6-diisopropylphenyl)- 1-[3-(4,7-dimethylindenyl)propyl]-imidazol-2-ylidene chromium methyl chloride and 3-(2,6- diisopropylphenyl)-1-[2-(4,7-dimethylindenyl)ethyl]-imidazol-2-ylidenevanadium dichloride. The following alkyl chromium complexes containing 1-[2-(4,7-dimethylindenyl)ethyl]-3-(2,6- diisopropylphenyl)imidazol-2 ylidene potassium have also been synthesised: 3-(2,6- diisopropylphenyl)-1-[2-(4,7-dimethylindenyl)ethyl]-imidazol-2-ylidene chromium phenyl chloride and 3-(2,6-diisopropyl-phenyl)-1-[2-(4, 7-dimethylindenyl)ethyl]-imidazol-2-ylidene chromium dibenzyl. Chromium cations have been synthesised using as starting materials the chromium alkyl complexes. The Cr(II) complex 3-(2,6-diisopropyl-phenyl)-1-[2-(4, 7- dimethylindenyl)ethyl]-imidazol-2-ylidene chromium monochloride and a partially oxidised dimerised product were also isolated. 5-(2-chloroethyl)- 1, 2, 3, 4-tetramethylcyclopentadiene and 5-(3-chloropropyl) 1, 2, 3, 4-tetramethylcyclopentadiene were synthesised and isolated as geminal isomers for the first time. The trialkyl chromium complex, tribenzyl chromium tris(tetrahydrofuran) was synthesised and also it was used as starting material for the complexes di(benzyl)chromium bis(1, 3- diisopropylimidazol-2-ylindene) and tri(benzyl)chromium TACN. All complexes were characterised by X-ray crystallography. The imidazolium salt 3-(2.6-diisopropylphenyl)-1-[N, N-bis(2,6- diisopropylphenyl)acetamidyl] imidazolium chloride was synthesised and used as a precursor for the synthesis of amidinate-functionalised NHC zirconium and amidine-functionalised NHC silver complexes. Double deprotonation of 3-(2,6-diisopropylphenyl)-1-[N, N'-bis(2,6- diisopropylphenyl)acetamidyl] imidazolium chloride gave the amidinate-functionalised NHC ligand, 3-(2.6-diisopropylphenyl)-1-[2-N, N'bis(2,6 diisopropylphenylamidinate)ethyl]imidazol-2-ylidenepotassium. Titanium, zirconium and chromium complexes containing this ligand were synthesised and characterised by X-ray crystallographic techniques. Transmetallation of the amidine-functionalised NHC silver complex with [Rh(COD)Cl]2 and [Ir(COD)Cl]2 gave the corresponding species. Rh(amidinefunctionalised NHC)(COD)Cl reacted with Na(BAr)4 (Ar = 3,5-CF3C6H3) to give the cation Rh(amidine-functionalised NHC)(COD)]+[BAr4]-. These species were also characterised by X-ray diffraction techniques.

Iron Catalysis

Iron Catalysis
Author: Bernd Plietker
Publisher: Springer Science & Business Media
Total Pages: 227
Release: 2011-01-05
Genre: Science
ISBN: 3642146694

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Juan I. Padrón and Víctor S. Martín: Catalysis by means of Fe-based Lewis acids; Hiroshi Nakazawa*, Masumi Itazaki: Fe–H Complexes in Catalysis; Kristin Schröder, Kathrin Junge, Bianca Bitterlich, and Matthias Beller: Fe-catalyzed Oxidation Reactions of Olefins, Alkanes and Alcohols: Involvement of Oxo- and Peroxo Complexes; Chi-Ming Che, Cong-Ying Zhou, Ella Lai-Ming Wong: Catalysis by Fe=X Complexes (X=NR, CR2); René Peters, Daniel F. Fischer and Sascha Jautze: Ferrocene and Half Sandwich Complexes as Catalysts with Iron Participation; Markus Jegelka, Bernd Plietker: Catalysis by Means of Complex Ferrates.

The Art of Writing Reasonable Organic Reaction Mechanisms

The Art of Writing Reasonable Organic Reaction Mechanisms
Author: Robert B. Grossman
Publisher: Springer Science & Business Media
Total Pages: 371
Release: 2007-07-31
Genre: Science
ISBN: 0387954686

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Intended for students of intermediate organic chemistry, this text shows how to write a reasonable mechanism for an organic chemical transformation. The discussion is organized by types of mechanisms and the conditions under which the reaction is executed, rather than by the overall reaction as is the case in most textbooks. Each chapter discusses common mechanistic pathways and suggests practical tips for drawing them. Worked problems are included in the discussion of each mechanism, and "common error alerts" are scattered throughout the text to warn readers about pitfalls and misconceptions that bedevil students. Each chapter is capped by a large problem set.

N-Heterocyclic Carbenes

N-Heterocyclic Carbenes
Author: Silvia Diez-Gonzalez
Publisher: Royal Society of Chemistry
Total Pages: 637
Release: 2016-11-04
Genre: Science
ISBN: 1782626816

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In less than 20 years N-heterocyclic carbenes (NHCs) have become well-established ancillary ligands for the preparation of transition metal-based catalysts. This is mainly due to the fact that NHCs tend to bind strongly to metal centres, avoiding the need of excess ligand in catalytic reactions. Also, NHC‒metal complexes are often insensitive to air and moisture, and have proven remarkably resistant to oxidation. This book showcases the wide variety of applications of NHCs in different chemistry fields beyond being simple phosphine mimics. This second edition has been updated throughout, and now includes a new chapter on NHC‒main group element complexes. It covers the synthesis of NHC ligands and their corresponding metal complexes, as well as their bonding and stereoelectronic properties and applications in catalysis. This is complemented by related topics such as organocatalysis and biologically active complexes. Written for organic and inorganic chemists, this book is ideal for postgraduates, researchers and industrialists.

The Vocabulary and Concepts of Organic Chemistry

The Vocabulary and Concepts of Organic Chemistry
Author: Milton Orchin
Publisher: John Wiley & Sons
Total Pages: 904
Release: 2005-07-08
Genre: Science
ISBN: 0471713732

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This book is a basic reference providing concise, accurate definitions of the key terms and concepts of organic chemistry. Not simply a listing of organic compounds, structures, and nomenclatures, the book is organized into topical chapters in which related terms and concepts appear in close proximity to one another, giving context to the information and helping to make fine distinctions more understandable. Areas covered include: bonding, symmetry, stereochemistry, types of organic compounds, reactions, mechansims, spectroscopy, and photochemistry.

Divalent Carbon

Divalent Carbon
Author: Jack Hine
Publisher:
Total Pages: 224
Release: 1964
Genre: Science
ISBN:

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Iron Catalysis in Organic Chemistry

Iron Catalysis in Organic Chemistry
Author: Bernd Plietker
Publisher: John Wiley & Sons
Total Pages: 295
Release: 2008-09-08
Genre: Science
ISBN: 3527623280

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This first comprehensive book to cover this exciting field also deals with the biological aspects, such as enzymes with iron. Following an introduction, this handy reference and handbook goes on to deal with reductions, oxidations of C, H- and C=C bonds, oxidative allylic oxygenation and amination, the oxidation of heteroatoms, cross coupling reactions, aromatic and nucleophilic substitutions, addition to carbonyl compounds, and cyclisations as well as ring opening reactions. The chapters are clearly classified according to the reaction type, allowing readers to quickly locate the desired information.

Hydrogen Transfer Reactions

Hydrogen Transfer Reactions
Author: Gabriela Guillena
Publisher: Springer
Total Pages: 393
Release: 2016-09-27
Genre: Science
ISBN: 3319430513

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The series Topics in Current Chemistry Collections presents critical reviews from the journal Topics in Current Chemistry organized in topical volumes. The scope of coverage is all areas of chemical science including the interfaces with related disciplines such as biology, medicine and materials science. The goal of each thematic volume is to give the non-specialist reader, whether in academia or industry, a comprehensive insight into an area where new research is emerging which is of interest to a larger scientific audience. Each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years are presented using selected examples to illustrate the principles discussed. The coverage is not intended to be an exhaustive summary of the field or include large quantities of data, but should rather be conceptual, concentrating on the methodological thinking that will allow the non-specialist reader to understand the information presented. Contributions also offer an outlook on potential future developments in the field.