The use of FeCl 2 (THF) 1.5 lead to the synthesis of [PhTt tB u]FeCl that provided entry into new [PhTt tBu]FeX chemistry. [PhTt tBu]FeCl crystallizes as a five-coordinate chloride bridged dimer that is a high-spin ferrous complex with an S = 2 ground state. The metathetical reaction of [PhTt tBu]FeCl with the desired dialkylmagnesium reagent, R 2 Mg (R = Me, Et, Ph, Bn), in 1,4-dioxane/THF leads to the formation of high-spin, S = 2, electronically and coordinatively unsaturated four-coordinate organoiron(II) complexes of the type, [PhTt tBu]Fe(R) (R = Me, Et, Ph, Bn). Reaction of [PhTt tBu]Fe(R) (R = Me, Et, Ph) with CO yields the low-spin, S = 0, six-coordinate complexes [PhTt tBu]Fe(CO) 2 (R) (R = Me, Et, Ph). Carbonylation of [PhTt tBu]Fe(Bn) yields [PhTt tBu]Fe(CO) 2 (Bn) and the reduced monovalent species [PhTt tBu]Fe(CO) 2 . The reduction of [PhTt tBu]FeCl in the presence of a phosphine ligand, PMe 3 or PEt 3, yields the high-spin, S = 3/2, monovalent iron complexes, [PhTt tBu]Fe(PMe 3) or [PhTt tBu]Fe(PEt 3) in moderate yields. [PhTt tBu]Fe(PMe 3) reacts with CO producing the low-spin, S = 1/2, monovalent product [PhTt tBu]Fe(CO) 2 . X-ray crystallographic analysis confirms a five-coordinate, square pyramidal coordination geometry. [PhTt tBu]Fe(PMe 3) reacts with diphenylacetylene producing the high-spin, S = 3/2 product [PhTt tBu]Fe(PhC=CPh). X-ray crystallography confirms a five-coordinate, square pyramidal coordination geometry with PhC=CPh bound to the iron center in a symmetric, side-on eta 2 binding mode. [PhTt tBu]Fe(PMe 3) reacts with adamantyl azide producing the high-spin, S = 3/2 product, [kappa 2 -PhTt tBu]Fe(N 4 Ad 2). The dialkyltetraazadiene ligand exhibits nearly identical N-N bonds suggesting a delocalized ligand radical dialkyltetraazadiene resonance form. Efforts to model a catalytically inhibited form of COdH were performed by designing a simple Ni:Fe binuclear complex that provides the essential metal coordination spheres of the C-cluster active site. The scope of these studies was expanded to include a series of cyanide-bridged binuclear complexes, ('S 3 ')Ni-CN-M[Tp tBu] (M = Fe, Co, Ni, Zn). A similar coupling scheme was used to synthesize the copper(I) analogue, Et 4 N{('S 3 ')Ni-CN-Cu[Tp tBu]}. Two synthetic strategies were employed to investigate the formation of cyanide-bridged linkage isomers. The products of two different 13 CN labeled reactions intended to yield ('S 3 ')Ni-CN-Zn[Tp tBu] and ('S 3 ')Ni-NC-Zn[Tp tBu] were analyzed. Nearly identical infrared and 13 C NMR spectroscopic data provide additional evidence that ('S 3 ')Ni-CN-Zn[Tp tBu] is produced in both reactions.

This thesis describes the synthesis and characterization of numerous metal-metal bonded complexes that are stabilized by extremely bulky amide ligands. It provides a comprehensive overview of the field, including discussions on groundbreaking complexes and reactions, before presenting in detail, exciting new findings from the PhD studies. The thesis appeals to researchers, professors and chemistry undergraduates with an interest in inorganic and/or organometallic chemistry.

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