On the Catalytic Efficacy of Low-Oxidation State Group 14 Complexes

On the Catalytic Efficacy of Low-Oxidation State Group 14 Complexes
Author: Terrance John Hadlington
Publisher: Springer
Total Pages: 256
Release: 2017-02-14
Genre: Science
ISBN: 3319518070

This outstanding thesis describes a detailed investigation into the use of low-oxidation-state group 14 complexes in catalysis, developed at the cutting edge of inorganic and organometallic chemistry. It includes the preparation of a number of landmark compounds, some of which challenge our current understanding of metal–metal bonding and low-oxidation-state main group chemistry. Among the many highlights of this thesis, the standout result is the development of the first well-defined, low- oxidation-state main group hydride systems as highly efficient catalysts in the hydroboration of carbonyl substrates, including carbon dioxide, which are as efficient as those observed in more traditional, transition-metal catalyses. These results essentially define a new subdiscipline of chemistry.

Studies of Low Oxidation State Group 14 Complexes and Their Reactivity Towards Small Molecules

Studies of Low Oxidation State Group 14 Complexes and Their Reactivity Towards Small Molecules
Author: Jiaye Li
Publisher:
Total Pages: 410
Release: 2013
Genre:
ISBN:

This thesis concerns research into the synthesis of low oxidation state group 14 complexes and their reactivity towards small molecule activation. A number of group 14 complexes in the +1 or +2 oxidation states have been synthesized. These include the first singly-bonded amido germanium(I) complex (amido-digermyne, [LGeGeL], L = {N(MeAr)(SiMe3)}, MeAr = C6H2{C(H)Ph2}2Me-2,6,4), amido group 14 metal(II) halide complexes, e.g. [LECl] (E = Ge, Sn or Pb, SiR3 = SiMe3, SiPh2Me or SiPh3), and amido silicon(IV) halide complexes, e.g. [LSiX3] (X = Cl or Br). The reactivity of the amido digermyne towards a variety of small molecules, e.g. H2, CO2, N2O, CS2, alkynes, etc., has been examined. In addition, the synthesis of "one-coordinate" group 14 metal(II) monocationic complexes (e.g. [LE]+[PF]-, E = Ge or Sn, PF = [Al{OC(CF3)3}4]- ) has been investigated and their reactivity towards Lewis base molecules has been examined. Work included in this thesis can be divided into six chapters. Chapter 1 introduces recent developments in main group chemistry, bonding in low oxidation state main group compounds, kinetic stabilization, and the "inert pair" effect. Some examples of low oxidation state main group complexes are described.Chapter 2 introduces the synthesis and coordination chemistry of a series of bulky secondary amines, [(MeAr)(SiR3)NH], [(iPrAr)(SiMe3)NH] (iPrAr = C6H2{C(H)Ph2}2iPr-2,6,4) and [(tBuAr)(SiR3)NH] (tBuAr = C6H2{C(H)Ph2}2tBu-2,6,4). Subsequently, the chapter discusses the synthesis of amido group 14 metal(II) halide complexes, e.g. [LECl] (E = Ge, Sn or Pb; SiR3 = SiMe3, SiPh2Me or SiPh3), [{(iPrAr)(SiMe3)N}ECl] (E = Ge or Sn) and {(tBuAr)(SiMe3)N}GeCl. The structures of these complexes have been determined using X-ray crystallography. Furthermore, amido silicon(IV) halide complexes, [LSiX3] (SiR3 = SiMe3, SiPh2Me or SiPh3; X = Cl or Br) and [{(iPrAr)(SiR3)N}SiBr3], as well as an amido silicon hydride, [LSi(H)Cl2] have been synthesized and structurally investigated. Chapter 3 discusses the synthesis and structural characterization of the first singly-bonded amido-digermyne, [LGeGeL], and its reactivity towards small gas molecule activation, e.g. that of H2, CO2, N2O, etc. at ambient and low temperatures. These reactions produced bulky amido germanium(II) and germanium(III) hydride complexes, and a bis(germylene) oxide complex. Further efforts have been devoted to the reactivity of [LGeGeL] towards molecules such as CS2, tBuNC and tBuNCO. Chapter 4 expands on the reactivity of [LGeGeL] and [L#GeGeL#] (L# = (iPrAr)(SiiPr3)N). It describes reactions that have been carried out with organic molecules, e.g. cyclooctatetraene (COT), 4-dimethylaminopyridine (DMAP), azobenzene, 1,4-bis(trimethylsilyl)butadiyne, norbornadiene, etc. These reactions produced a number of low oxidation state germanium complexes. In general, the reactions of [LGeGeL] and [L#GeGeL#] with unsaturated molecules produced products with the substrate inserted into the Ge-Ge bond. However, the reaction with DMAP produced a bis-adducted germanium complex with a shortened Ge-Ge bond. Finally, reactions of [LGeGeL] with chlorinated compounds, iodine, and ketones are discussed. Chapter 5 summarizes investigations into the synthesis and coordination chemistry of the first examples of bulky amido "one-coordinate" germanium(II) and tin(II) monocationic complexes, [LE]+[PF]- (E = Ge or Sn, PF = [Al{OC(CF3)3}4]-) and [L'Sn]+[PF]- (L' = [(MeAr)(SiPh2Me)N]). Their reactivity towards DMAP was investigated, and this led to two-coordinate adducted germanium or tin cationic complexes. Chapter 6 summarizes miscellaneous results, and consists of two sections. The first section discusses theoretical investigations into the Mo-Ge bonding of singly-bonded or triply-bonded molybdenum germylene and germylyne complexes. Wiberg bond indices (WBI) were acquired to provide a quantitative description of the bonding in these complexes. The second section focuses on investigations into the synthesis of a bulky gallium(I) amide complex, [LGa:], which was prepared from the reaction of [{(MeAr)(SiMe3)N}Li] and "GaI". X-ray crystallographic studies of [LGa:] were carried out and indicate that the complex is essentially one-coordinate.

Redox-Active Ligands

Redox-Active Ligands
Author: Marine Desage-El Murr
Publisher: John Wiley & Sons
Total Pages: 373
Release: 2024-01-31
Genre: Science
ISBN: 352783088X

Redox-Active Ligands Authoritative resource showcasing a new family of ligands that can lead to better catalysts and promising applications in organic synthesis Redox-Active Ligands gives a comprehensive overview of the unique features of redox-active ligands, describing their structure and synthesis, the characterization of their coordination complexes, and important applications in homogeneous catalysis. The work reflects the diversity of the subject by including ongoing research spanning coordination chemistry, organometallic chemistry, bioinspired catalysis, proton and electron transfer, and the ability of such ligands to interact with early and late transition metals, lanthanides, and actinides. The book is divided into three parts, devoted to introduction and concepts, applications, and case studies. After the introduction on key concepts related to the field, and the different types of ligands and complexes in which ligand-centered redox activity is commonly observed, mechanistic and computational studies are described. The second part focuses on catalytic applications of redox-active complexes, including examples from radical transformations, coordination chemistry and organic synthesis. Finally, case studies of redox-active guanidine ligands, and of lanthanides and actinides are presented. Other specific sample topics covered include: An overview of the electronic features of redox-active ligands, covering their historical perspective and biological background The versatility and mode of action of redox-active ligands, which sets them apart from more classic and tunable ligands such as phosphines or N-heterocyclic carbenes Preparation and catalytic applications of complexes of stable N-aryl radicals Metal complexes with redox-active ligands in H+/e- transfer transformations By providing up-to-date information on important concepts and applications, Redox-Active Ligands is an essential reading for researchers working in organometallic and coordination chemistry, catalysis, organic synthesis, and (bio)inorganic chemistry, as well as newcomers to the field.

Comprehensive Inorganic Chemistry II

Comprehensive Inorganic Chemistry II
Author:
Publisher: Newnes
Total Pages: 7694
Release: 2013-07-23
Genre: Science
ISBN: 0080965296

Comprehensive Inorganic Chemistry II, Nine Volume Set reviews and examines topics of relevance to today’s inorganic chemists. Covering more interdisciplinary and high impact areas, Comprehensive Inorganic Chemistry II includes biological inorganic chemistry, solid state chemistry, materials chemistry, and nanoscience. The work is designed to follow on, with a different viewpoint and format, from our 1973 work, Comprehensive Inorganic Chemistry, edited by Bailar, Emeléus, Nyholm, and Trotman-Dickenson, which has received over 2,000 citations. The new work will also complement other recent Elsevier works in this area, Comprehensive Coordination Chemistry and Comprehensive Organometallic Chemistry, to form a trio of works covering the whole of modern inorganic chemistry. Chapters are designed to provide a valuable, long-standing scientific resource for both advanced students new to an area and researchers who need further background or answers to a particular problem on the elements, their compounds, or applications. Chapters are written by teams of leading experts, under the guidance of the Volume Editors and the Editors-in-Chief. The articles are written at a level that allows undergraduate students to understand the material, while providing active researchers with a ready reference resource for information in the field. The chapters will not provide basic data on the elements, which is available from many sources (and the original work), but instead concentrate on applications of the elements and their compounds. Provides a comprehensive review which serves to put many advances in perspective and allows the reader to make connections to related fields, such as: biological inorganic chemistry, materials chemistry, solid state chemistry and nanoscience Inorganic chemistry is rapidly developing, which brings about the need for a reference resource such as this that summarise recent developments and simultaneously provide background information Forms the new definitive source for researchers interested in elements and their applications; completely replacing the highly cited first edition, which published in 1973

Advances in Organic Synthesis

Advances in Organic Synthesis
Author: Atta-ur-Rahman
Publisher: Bentham Science Publishers
Total Pages: 513
Release: 2013-03-27
Genre: Science
ISBN: 1608050297

Advances in Organic Synthesis is a book series devoted to the latest advances in synthetic approaches towards challenging structures. It presents comprehensive articles written by eminent authorities on different synthetic approaches to selected target molecules and new methods developed to achieve specific synthetic transformations. Contributions are written by eminent scientists and each volume is edited by an authority in the field. Advances in Organic Synthesis is essential for all organic chemists in the academia and industry who wish to keep abreast of rapid and important developments in the field.

Modern Organonickel Chemistry

Modern Organonickel Chemistry
Author: Yoshinao Tamaru
Publisher: John Wiley & Sons
Total Pages: 346
Release: 2006-03-06
Genre: Science
ISBN: 3527604235

Organonickel chemistry plays an increasingly important role in organic chemistry, and interest in this topic is now just as keen as in organopalladium chemistry. While there are numerous, very successful books on the latter, a book specializing in organonickel chemistry is long overdue. Edited by one of the leading experts in the field, this volume covers the many discoveries made over the past 30 years, and previously scattered throughout the literature. Active researchers working at the forefront of organonickel chemistry provide a comprehensive review of the topic, including cross-coupling reactions, asymmetric synthesis and heterogeneous catalysis reaction types. A must-have for both organometallic chemists and synthetic organic chemists.

Comprehensive Organometallic Chemistry III, Volume 5

Comprehensive Organometallic Chemistry III, Volume 5
Author: D. M. P. Mingos
Publisher:
Total Pages: 1008
Release: 2007
Genre: Science
ISBN:

Provides essential information for any chemist or technologist who needs to use or apply organometallic compounds. Provides a comprehensive overview of recent developments in the field and attempts to predict trends in the field over the next ten years.