| This thesis is an investigation of the formation of metal-sulfur bonds, starting from simple, readily available starting materials. The precursors are generally metal-oxo or metal halide complexes, and the protocols that have been developed to synthesize target compounds are easily accomplished using standard Schlenk or inert atmosphere glovebox techniques. The focus is mainly on the biologically relevant metals molybdenum and tungsten, but other transitions metals have been used as well to expand the scope of the synthetic methodology.;Chapter 1 explores the reactivity of triamine-ligated molybdenum- and tungsten trioxide complexes. The supporting triamine ligation is relatively inert, allowing the observation of reactivity for the metal-trioxide unit as an independent functional group. The nucleophilicity of these metal trioxide units has been explored by the reaction with strong electrophiles. In some cases, stable electrophilec addition products form with partial cleavage of metal-oxo bonds, whereas other reagents enable direct sulfur-for-oxo substitution.;Chapter 2 probes the reactivity of metal tetroxide anions (M = Mo, W, Re) with strong electrophiles. Organosilicon reagents in particular react with these tetroxide anions to effect non-aqueous substitution of terminal sulfido or ene-1,2-dithiolate ligands for terminal oxo ligands. Syntheses can be performed at room temperature or below, allowing for the controlled substitution of terminal oxo ligands.;Chapter 3 extends the methodology developed in Chapter 2 for the synthesis of dithiolene-ligated transition metal complexes to other metals in addition to, and including, molybdenum, tungsten, and rhenium. The use of dialkyldithiolene ligands instead of the 1,2-benzenedithiolate ligand in this investigation are of interest to this laboratory. The use of metal halide and metal oxyhalide complexes as synthetic precursors makes this methodology both pragmatically and financially attractive. |
