The entire set of analogous mono-indenyl metal trichlorides have been prepared for the titanium triad metals, (715-C9H7)TiC13, [(715-C9H7)ZrCI(.t-Cl)2]X, [(715-C9H7)HfCl2(µCl)]2. The interaction of (715-C9H7)TiCl3 and [(715-C9H7)HfC12(p.-Cl)]2 with A1Me3 hasled to the isolation and characterization of (715-C9H7)TiCH3C12 and [(715C9H7)HfCH3C1(µ-C1)]2, respectively. Also, the unexpected production of (715C9H7)2Ti(CH3)2 from the reaction of (715-C9H7)TiCl3 with LiMe has been examined. The reactivity of (715-C9H7)TiC13, [(715-C9H7)ZrCl(µ-Cl)2]X, and [(715-C9H7)HfC12(9-Cl)]2 with various Lewis bases has been explored and has afforded the isolation and characterization of the unusual half-sandwich phosphine complexes (C9H7)TiC13(PMe3), (715-C9H7)ZrC13(PMe3)2, (715-C9H7)HfC13(PMe3)2, and (715-C9H7)HfC13(PMe3) as well as (T15-C9H7)ZrC13(DME) and (715-C9H7)HfCI3(DME). Several examples of indenyl-metal bond cleavage have been observed. The indenyl-imido complex, [(715-C9H7)TiCI(p.NCH3)]2, has also been synthesized. The crystal structures of (715-C9H7)TiC13, [(715C9H7)HfC12(p.-Cl)]2, [(715-C9H7)HfCH3C1(µ-Cl)]2, and (715-C9H7)HfC13(PMe3) have been determined. / Department of Chemistry

The preparation of tri-n-butylstannylindene, has led to new synthetic routes to obtaining indenyl metal complexes of the Group V metal halides. Also, the fluxional behavior of tri-n-butylstannylindene has been studied by variable temperature 1H NMR spectroscopy.The interaction of the Group V metal halides with tri-n-butylstannylindene has led to the isolation and characterization of [(q5-C9H7)2TaC12] [TaC16] and [('q5-C9H7)2NbC12] [NbCl6]. Subsequent Lewis base chemistry has produced (T15-C9H7)TaC14(PMe3). The crystal structures of [(r15-C9H7)2TaCl2] [TaC16] and (15-C9H7)TaC14(PMe3) have been determined. The preparation and characterization of these compounds are discussed as well as the exploratory indenyl, Lewis base, and /or salt chemistry of vanadium, niobium, and tantalum. / Department of Chemistry