Group 11 transition metals are used daily throughout our bodies and as additives in many common products. One biological function of copper, a group 11 metal, is its use in the Cu A site of cytochrome c oxidase, an enzyme found in the last step of cellular respiration. To model this active site, three formamidinate ligands have been examined: 2,6-dimethylphenyl, 2,6- diisopropylphenyl, and 2,4,6-trimethylphenyl. The synthesis and structural characterization of these dinuclear Cu(I) complexes is described as well as their redox chemistry with I 2 to afford complexes of mixed-valence which is the normal resting state of the Cu A site. Using EPR spectroscopy and DFT calculations on the iodine oxidized products, different electronic structures base d on the formamidinate was found. Additionally, insertion of CS 2 into the copper-nitrogen bonds of the copper(I) formamidinate complexes produces tetra- and hexanuclear clusters based on the steric properties of the ligand

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.

Presented herein are the isolation and characterization of a number of new copper(I) halide complexes and the first two examples of monomeric copper(I) amido complexes, (dtbpe)Cu(NHPh) and (IPr)Cu(NHPh). These Cu(I) anilido complexes have been shown to be more nucleophilic than a related Ru(II) anilido complex in reactivity studies with bromoethane, and reveal increasing nucleophilicity in the order (SIPr)Cu(NHPh) < (IPr)Cu(NHPh) < (IMes)Cu(NHPh) < (dtbpe)Cu(NHPh). (IPr)Cu(NHPh) is thermodynamically favored over (IPr)Cu(Ph)/NH2Ph or [(IPr)Cu(mu-H)]2/NH2Ph, respectively. Computational studies are consistent with the observed reactivity and indicate strong Cu-N bonds with nucleophilic amido nitrogen.

Keywords: hydroamination, copper(I), platinum(IV), platinum(II), hydroalkoxylation, hydrothiolation, C-H activation.

Almost all branches of chemistry and material science now interface with organometallic chemistry--the study of compounds containing carbon-metal bonds. This widely acclaimed serial contains authoritative reviews that address all aspects of organometallic chemistry, a field that has expanded enormously since the publication of Volume 1 in 1964. - Informs and updates on all the latest developments in the field - Contributions from leading authorities and industry experts

This book reflects the increasing interest among the chemical synthetic community in the area of asymmetric copper-catalyzed reactions, and introduces readers to the latest, most significant developments in the field. The contents are organized according to reaction type and cover mechanistic and spectroscopic aspects as well as applications in the synthesis of natural products. A whole chapter is devoted to understanding how primary organometallics interact with copper to provide selective catalysts for allylic substitution and conjugate addition, both of which are treated in separate chapters. Another is devoted to the variety of substrates and experimental protocols, while an entire chapter covers the use on non-carbon nucleophiles. Other chapters deal with less-known reactions, such as carbometallation or the additions to imines and related systems, while the more established reactions cyclopropanation and aziridination as well as the use of copper (II) Lewis acids are warranted their own special chapters. Two further chapters concern the processes involved, as determined by mechanistic studies. Finally, a whole chapter is devoted to the synthetic applications. This is essential reading for researchers at academic institutions and professionals at pharmaceutical or agrochemical companies.