This thesis addresses the coordination chemistry and reactivity of copper and gold complexes with a focus on the elucidation of (i) the metal-mediated activation of σ-bonds and (ii) the migratory insertion reaction. Both processes are of considerable importance in organometallic chemistry, but remain elusive for Cu and Au complexes. In this work, the author contributes significant advances: The first σ-SiH complexes of copper are experimentally and computationally characterized, yielding valuable insights into σ-bond activation processes for copper. Evidence for a highly unusual migratory syn insertion of unsaturated organic molecules into the gold-silicon bond of silylgold (I) complexes is provided and the corresponding mechanism identified. The intermolecular oxidative addition of σ-SiSi, σ-CC and σ-CX (X=halogen) bonds with molecular gold (I) complexes is studied in detail, effectively demonstrating that this reaction, usually considered to be impossible for gold, is actually highly favored, provided an adequate ligand is employed. The use of small-bite angle bis (phosphine) gold (I) complexes allows for the first time the oxidative addition of σ-CC and σ-CX bonds for gold (I). These results shed light on an unexpected reactivity pattern of gold complexes and may point the way to 2-electron redox transformations mediated by this metal, opening up new perspectives in gold catalysis.

Direct Synthesis of Metal Complexes provides in-depth coverage of the direct synthesis of coordination and organometallic compounds. The work is primarily organized by methods, but also covers highly relevant complexes, such as metal-polymer coordination compounds. This updated reference discusses recent developments in cryosynthesis, electrosynthesis, and tribosynthesis (popular as it doesn't require organic solvents), with special attention paid to 'greener' methodologies and approaches. Additionally, the book describes physical methods of zero-valent metal interaction with organic matter, including sputtering, ultrasonic treatment and synthesis in ionic liquids. The book presents completely new content as a follow-up to the 1999 Elsevier Science publication Direct Synthesis of Coordination and Organometallic Compounds that was edited by Dr. Garnovskii and Dr. Kharisov. - Covers current methods and techniques of metal interactions with organic media leading to metal chelates, adducts, di- and polymetallic complexes, metal-containing macrocycles, supported coordination compounds (i.e., metal complexes on carbon nanotubes), and more - Describes reactivities of distinct forms of elemental metals (powders, sheets, nanoparticles (including a host of less-common metal nanostructures) with organic phase (liquid, solid and gaseous) and water - Includes experimental procedures, with examples of direct synthesis, at the end of each chapter

The present work is a study concerning the coordination chemistry and reactivity of copper and gold complexes. Of particular interest was the elucidation of (i) the metal-mediated activation of s-bonds and (ii) the migratory insertion reaction. Both processes are of considerable importance in organometallic chemistry, but elusive for copper and gold. The first part of this manuscript is dedicated to the study of the coordination of s-SiH bonds to copper. By means of a chelate assistance approach, we synthesized copper complexes employing diphosphino-hydrosilane ligands (R2P(o-C6H4))2Si(R')H. This study allowed for the identification of a weak ?2-SiH coordination to copper that has been evidenced by experimental (NMR, IR, XRD) and computational (geometry optimization, NBO analysis) means. The s-SiH coordination is essentially dominated by donation of electron density from the hydrosilane moiety to copper, without significant backdonation. In the second part, we investigated the reactivity of silylgold(I) complexes towards unsaturated organic molecules. We showed that these complexes react with alkynes and allenes to yield (Beta-silyl)vinylgold complexes via migratory syn insertion into the gold-silicon bond. A mechanistic proposal consisting of a 2-step coordination insertion process was established for this transformation by means of a kinetic and computational study. In the third part, the intermolecular oxidative addition of s-SiSi, s-CC and s-CX (X=halogen) bonds with molecular gold(I) complexes was studied in detail. We showed that this reaction, usually considered to be impossible for gold, is actually highly favored, provided an adequate ligand is employed. Disilanes add to cationic monophosphine gold(I) complexes. However, the corresponding bis(silyl)gold(III) products are highly unstable. The use of bis(phosphine) gold(I) complexes, featuring a bidentate ligand with a small bite-angle, allowed for the first time for the oxidative addition of s-CC and s-CX bonds at gold(I) and proved key for the stabilization of the corresponding gold(III) products that were characterized by spectroscopic and structural means. These results shed light on an unexpected reactivity pattern of gold complexes and may be an entry point to 2-electron redox transformations mediated by this metal, opening up new perspectives in gold catalysis.

Modern techniques to produce nanoparticles, nanomaterials, and nanocomposites are based on approaches that frequently involve high costs, inefficiencies, and negative environmental impacts. As such, there has been a real drive to develop and apply approaches that are more efficient and benign. The Handbook of Greener Synthesis of Nanomaterials and Compounds provides a comprehensive review of developments in this field, combining foundational green and nano-chemistry with the key information researchers need to assess, select and apply the most appropriate green synthesis approaches to their own work.Volume 1: Fundamental Principles and Methods provides a clear introduction to the fundamentals of green synthesis that places synthesis in the context of green chemistry. Beginning with a discussion of key greener physical and chemical methods for synthesis, including ultrasound, microwave and mechanochemistry methods, the book goes on to explore biological methods, including biosynthesis, green nanoformation, and virus-assisted methods. - Discusses synthesis in the context of the principles of green chemistry - Highlights both traditional and innovative technologies for the synthesis of nanomaterials and related composites under green chemistry conditions - Reflects on the current and potential applications of natural products chemistry in synthesis

This first handbook to focus solely on the application of N-heterocyclic carbenes in synthesis covers metathesis, organocatalysis, oxidation and asymmetric reactions, along with experimental procedures. Written by leading international experts this is a valuable and practical source for every organic chemist.

Organic Reaction Mechanisms 2019, the 55th annual volume in this highly successful and unique series, surveys research on organic reaction mechanisms described in the available literature dated 2019. The following classes of organic reaction mechanisms are comprehensively reviewed: Reaction of Aldehydes and Ketones and their Derivatives Reactions of Carboxylic, Phosphoric, and Sulfonic Acids and their Derivatives Oxidation and Reduction Carbenes and Nitrenes Nucleophilic Aromatic Substitution Electrophilic Aromatic Substitution Carbocations Nucleophilic Aliphatic Substitution Carbanions and Electrophilic Aliphatic Substitution Elimination Reactions Polar Addition Reactions Cycloaddition Reactions Molecular Rearrangements Radicals An experienced team of authors compile these reviews every year, so that the reader can rely on a continuing quality of selection and presentation.

Very small particles are able to show astonishing properties. For example, gold atoms can be combined like strings of pearls, while nanoparticles can form one-, two- and three-dimensional layers. These assemblies can be used, for instance, as semiconductors, but other electronic as well as optical properties are possible. An introduction to the booming field of "nanoworld" or "nanoscience", from fundamental principles to their use in novel applications. With its clear structure and comprehensive coverage, backed by numerous examples from recent literature, this is a prime reference for chemists and materials scientists working with and developing nanoparticle systems. A bestselling title in its second edition. A must-have reference for chemists and materials scientists.