Synthesis and Characterization of Reduced Ternary Molybdenum Oxides and Soluble Copper (III) Alkoxide Complexes [Dissertation]

This research work involves both solid state and solution chemistry. In the area of solid state chemistry, a number of exciting reduced ternary molybdenum oxides containing both discrete oligomeric cluster units K₃Mo₁₄O₂₂(1) and BaMo₅O₈ (2)) and infinite metal-metal bonded chains (KMo₄O₆ (3) and Sr_0.62Mo₄O₆ (4)) were discovered. Compound 1 contains discrete oligomeric units of three trans-edge-shared Mo₆ octahedra interconnected by Mo-O-Mo bonding to form chains along the monoclinic c-axis. The discrete oligomeric cluster units contained in compound 2 (Ba₂Mo₁₀O₁₆) are trans-edge-shared Mo₁₀ bioctahedral clusters interconnected along the a-axis of the monoclinic cell. The couplings between oligomeric clusters in compounds 1 and 2 are identical and can be described by the general formula Mo_4n+2O_6n+2O_4/2, where n is the number of Mo₆ octahedra trans-edge-fused together. Compounds 3 and 4 are members of this series with the infinite chain of trans-edge-shared Mo₆ octahedral cluster units. All the compounds reported so far are structurally characterized by [Mo₄O₆] octahedral cluster chains which are coupled through Mo-O-Mo interchain linkages to weave a puckered square pattern (except the case of KMo₄O₆ where a square pattern is formed) and form channels parallel to the chain axis in which the ternary metal ions are located. In the area of copper(ll) alkoxide chemistry, several interesting complexes with the anion of 2-(2-hydroxyethyl)pyridine (hep) as ligands have been synthesized and structurally characterized. The partially characterized compounds K_0.5M_1.9Mo₁₄O₂₂ (M = Ca, Sr, Ba, Pb and Sn), Ca_3-xMo₁₄O₂₂, Sn_3.6Mo₁₆O₂₄, PbMo₆O₁₀, and a novel copper(ll) alkoxide complex are also reported in this work.