Synthesis and characterization of novel group VI metal (Mo, W) nitride and oxide compounds

Investigations into the preparation of tungsten nitrides have involved the synthesis of molecular precursors, and their conversion to tungsten nitrides at relatively low temperatures. Two interesting molecular precursors, [WNCl{sub 3}{center_dot}NCCH{sub 3}]{sub 4} and WN(N{sub 3}){sub 3}{center_dot}xNCCH{sub 3}, have been prepared and characterized. The molecular structure of the first consists of a W{sub 4}N{sub 4} tetrameric core with multiple and single W-N bonds arranged in an alternating fashion. Three new solid state phases, amorphous W{sub 3}N{sub 5}, cubic WN, and W{sub 2}N{sub 2}(C{sub 2}N{sub 2}), have been discovered by solid state and chemical vapor transport reactions. The structures have been investigated. A systematic study in the Ln{sub 2}O{sub 3}-MoO{sub 3}-Mo (Ln = La, Ce, Pr, Nd, Sm) system has been explored to better understand LnMo{sub 8}O{sub 14}. The study has shown that the sizes of the rare-earth cations affect the formation of these phases. Larger cations (La, Ce, and Pr) aid in the formation of trans-Mo{sub 8} bicapped octahedra, and the smaller cations (Nd, Sm) only stabilize the cis-Mo{sub 8} bicapped octahedra. Magnetic susceptibility measurements have indicated that no effective moment contribution arises from the Mo{sub 8} metal clusters, even though the cis-Mo{sub 8} cluster in LnMo{sub 8}O{sub 14}, containing all cis-Mo{sub 8} octahedra, apparently contains an odd number of electrons (23). Electrical resistivity measurements and electronic structure calculations have shown that the LnMo{sub 8}O{sub 14} compounds containing cis-Mo{sub 8} clusters are metallic, and the LnMo{sub 8}O{sub 14} compounds containing a 1:1 ratio of cis- to trans-Mo{sub 8} clusters are semiconducting.