Rhodium and Iridium Complexes Supported by Chelating Bis-N-heterocyclic Carbene Ligands

Rhodium and Iridium Complexes Supported by Chelating Bis-N-heterocyclic Carbene Ligands PDF Author: Roxy Joanne Lowry
Publisher:
ISBN:
Category :
Languages : en
Pages :

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ABSTRACT: Eighty-five percent of all industrial chemical processes occur catalytically. The world's expanding appetite for mass production of exotic chemicals necessitates the design and application of enhanced catalysts. To optimize catalytic materials, the detailed relationships between catalyst architecture and reactivity must be determined. Although for many ligand families these relationships are well understood, novel catalysts require in depth empirical investigation to determine these connections. The design of a novel di-N-heterocyclic carbene family of ligands in reported herein. These C2 symmetric ligands are based on the rigid 9,10-dihydro-9,10-ethanoanthracene backbone and designed for utilization in chiral catalysis. Thorough investigation into the relationships between the ligand's structure and the architecture of the resulting rhodium and iridium catalysts directed the design of three generations of our novel ligand family. The first generation, trans-1,1'-[9,10-dihydro-9,10-ethanoanthracene-11,12- diyldimethanediyl]bis(benzylimidazole) bis(triflouromethansulfonate) [DEAM-BI](OTf)2 (2-1), is too flexible to enforce a rigid chiral pocket about a metal center under catalytic conditions. The constrained second generation ligands, trans-1,1'-(9,10-dihydro-9,10-ethanoanthracene.

Rhodium and Iridium Complexes Supported by Chelating Bis-N-heterocyclic Carbene Ligands

Rhodium and Iridium Complexes Supported by Chelating Bis-N-heterocyclic Carbene Ligands PDF Author: Roxy Joanne Lowry
Publisher:
ISBN:
Category :
Languages : en
Pages :

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Book Description
ABSTRACT: Eighty-five percent of all industrial chemical processes occur catalytically. The world's expanding appetite for mass production of exotic chemicals necessitates the design and application of enhanced catalysts. To optimize catalytic materials, the detailed relationships between catalyst architecture and reactivity must be determined. Although for many ligand families these relationships are well understood, novel catalysts require in depth empirical investigation to determine these connections. The design of a novel di-N-heterocyclic carbene family of ligands in reported herein. These C2 symmetric ligands are based on the rigid 9,10-dihydro-9,10-ethanoanthracene backbone and designed for utilization in chiral catalysis. Thorough investigation into the relationships between the ligand's structure and the architecture of the resulting rhodium and iridium catalysts directed the design of three generations of our novel ligand family. The first generation, trans-1,1'-[9,10-dihydro-9,10-ethanoanthracene-11,12- diyldimethanediyl]bis(benzylimidazole) bis(triflouromethansulfonate) [DEAM-BI](OTf)2 (2-1), is too flexible to enforce a rigid chiral pocket about a metal center under catalytic conditions. The constrained second generation ligands, trans-1,1'-(9,10-dihydro-9,10-ethanoanthracene.

Synthesis and Reactions of Complexes of Rhodium and Iridium Having Chelating N,O-donor Ligands

Synthesis and Reactions of Complexes of Rhodium and Iridium Having Chelating N,O-donor Ligands PDF Author: Namadzavho Enos Sitabule
Publisher:
ISBN:
Category : Rhodium
Languages : en
Pages : 302

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Metal Complexes

Metal Complexes PDF Author: Xue Duan
Publisher: Springer
ISBN: 9783540104940
Category : Science
Languages : en
Pages : 204

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Pincer and Chelate N-heterocyclic Carbene Complexes of Iridium, Palladium, and Rhodium

Pincer and Chelate N-heterocyclic Carbene Complexes of Iridium, Palladium, and Rhodium PDF Author: John Ronald Miecznikowski
Publisher:
ISBN:
Category :
Languages : en
Pages : 478

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Development of Novel Rhodium and Iridium Complexes with a Fac-chelating Ligand for Electrophilic C-H Activation

Development of Novel Rhodium and Iridium Complexes with a Fac-chelating Ligand for Electrophilic C-H Activation PDF Author: Jennifer Lee Rhinehart
Publisher:
ISBN:
Category :
Languages : en
Pages : 218

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"Several new bis-3,5(dimethylpyrazol-1-yl)acetate rhodium and iridium complexes were synthesized from MCl3?H2O. [Rh(bdmpza)Cl3]- was isolated with three different cations, lithium, sodium and tetraethylamonium, to obtain a full characterization profile. Analogously, [Ir(bdmpza)Cl3]- was isolated with two different cations, lithium and sodium, and characterized by 1H NMR, 13C NMR, elemental analysis and X-ray crystal structure determination. A neutral rhodium complex, [Rh(bdmpza)Cl2(py)], was also isolated as two isomers by addition of pyridine. Reaction of [Rh(bdmpza)Cl3]- and [Rh(bdmpza)Cl2(py)] with dimethylzinc afforded three new complexes, [Rh(bdmpza)Cl2(Me)]-, [Rh(bdmpza)Cl(Me)2]- and [Rh(bdmpza)Cl(Me)(py)]. Stoichiometric and catalytic C-H activation of benzene was investigated for these new rhodium methyl complexes. Novel rhodium and iridium precatalysts catalysts, [Rh(bdmpza)Cl3]- Na+, [Ir(bdmpza)Cl3]- Na+ and [Rh(bdmpza)Cl2(py)], were subjected to H/D exchange conditions with benzene and deuterated trifluoroacetic acid, acetic acid and methanol in the presence of a halide abstractor. Optimum conditions of silver triflate, deuterated trifuoroacetic acid, 100°C and 24 hours were identified to conduct arene H/D exchange studies. Most arenes investigated showed modest H/D exchange in the ring, while branched [beta]-sp3C-H bonds also showed affinity for H/D exchange. Mechanistic studies of [beta]-sp3C-H H/D exchange were carried out, including synthesis of [Rh(bdmpz)Cl3(py)], which does not contain the pendant acetate group"--Leaf vi.

N-Heterocyclic Carbenes

N-Heterocyclic Carbenes PDF Author: Silvia Diez-Gonzalez
Publisher: Royal Society of Chemistry
ISBN: 1782626816
Category : Science
Languages : en
Pages : 637

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Book Description
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.

Chemistry of Iron

Chemistry of Iron PDF Author: J. Silver
Publisher: Springer Science & Business Media
ISBN: 9401121400
Category : Science
Languages : en
Pages : 316

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Book Description
This book is designed to be of use to the reader in two different ways. First, it is intended to provide a general introduction to all aspects of iron chemistry for readers from a variety of different scientific backgrounds. It has been written at a level suitable for use by graduates and advanced undergraduates in chemistry and biochemistry, and graduates in physics, geology, materials science, metallurgy and biology. It is not designed to be a dictionary of iron compounds but rather to provide each user with the necessary tools and background to pursue their ,individual interests in the wide areas that are influenced by the chemistry of iron. To achieve this goal each chapter has been written by a contemporary expert active in the subject so that the reader will benefit from their individual insight. Although it is generally assumed that the reader will have an understanding of bonding theories and general chemistry, the book is well referenced so that any deficiencies in the reader's background can be addressed. The book was also designed as a general reference book for initial pointers into a scientific literature that is growing steadily as the understanding and uses of this astonishingly versatile element continue to develop. To meet this aim the book attempts some coverage of all aspects of the chemistry of iron, not only outlining what understanding has been achieved to date but also identifying targets to be aimed at in the future.

CO2 Hydrogenation Catalysis

CO2 Hydrogenation Catalysis PDF Author: Yuichiro Himeda
Publisher: John Wiley & Sons
ISBN: 3527346635
Category : Technology & Engineering
Languages : en
Pages : 322

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Book Description
A guide to the effective catalysts and latest advances in CO2 conversion in chemicals and fuels Carbon dioxide hydrogenation is one of the most promising and economic techniques to utilize CO2 emissions to produce value-added chemicals. With contributions from an international team of experts on the topic, CO2 Hydrogenation Catalysis offers a comprehensive review of the most recent developments in the catalytic hydrogenation of carbon dioxide to formic acid/formate, methanol, methane, and C2+ products. The book explores the electroreduction of carbon dioxide and contains an overview on hydrogen production from formic acid and methanol. With a practical review of the advances and challenges in future CO2 hydrogenation research, the book provides an important guide for researchers in academia and industry working in the field of catalysis, organometallic chemistry, green and sustainable chemistry, as well as energy conversion and storage. This important book: Offers a unique review of effective catalysts and the latest advances in CO2 conversion Explores how to utilize CO2 emissions to produce value-added chemicals and fuels such as methanol, olefins, gasoline, aromatics Includes the latest research in homogeneous and heterogeneous catalysis as well as electrocatalysis Highlights advances and challenges for future investigation Written for chemists, catalytic chemists, electrochemists, chemists in industry, and chemical engineers, CO2 Hydrogenation Catalysis offers a comprehensive resource to understanding how CO2 emissions can create value-added chemicals.

The Chemistry of Pincer Compounds

The Chemistry of Pincer Compounds PDF Author: David Morales-Morales
Publisher: Elsevier
ISBN: 0080545157
Category : Science
Languages : en
Pages : 467

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Book Description
Pincer complexes are formed by the binding of a chemical structure to a metal atom with at least one carbon-metal bond. Usually the metal atom has three bonds to a chemical backbone, enclosing the atom like a pincer. The resulting structure protects the metal atom and gives it unique properties.The last decade has witnessed the continuous growth in the development of pincer complexes. These species have passed from being curiosity compounds to chemical chameleons able to perform a wide variety of applications. Their unique metal bound structures provide some of the most active catalysts yet known for organic transformations involving the activation of bonds. The Chemistry of Pincer Compounds details use of pincer compounds including homogeneous catalysis, enantioselective organic transformations, the activation of strong bonds, the biological importance of pincer compounds as potential therapeutic or pharmaceutical agents, dendrimeric and supported materials.* Describes the chemistry and applications of this important class of organometallic and coordination compounds* Covers the areas in which pincer complexes have had an impact* Includes information on more recent and interesting pincer compounds not just those that are well-known

Synthesis and Characterization of Rhodium and Iridium Complexes with the Bis(dimethylsilylcyclopentadienyl) Ligand

Synthesis and Characterization of Rhodium and Iridium Complexes with the Bis(dimethylsilylcyclopentadienyl) Ligand PDF Author: Gordon J. Hunter
Publisher:
ISBN:
Category : Dissertations, Academic
Languages : en
Pages : 66

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Book Description