The interaction of TiX4 (X= Cl and Br) with 1-(trimethylsilyl) indene or 1(tributylstannyl) indene results in the formation of the crystalline trihalide complexes (rl5C9H7 )TiX3 in excellent yield. Isolation of these complexes has provided pathways for the monoalkyl complexes (TI5-C9H7 )TiX2 reaction of (r15-C9H7 )TiX3 (X = Cl and Br) withtrimethylaluminum resulted in the formation of the crystalline monomethyl complexes (Tl5C9H7 )TiX2R in good yield. Isolating these complexes free of the dimethyl derivativeproved difficult in normal alkylating solvents, but the pure monomethyl species were isolated in high yields when the reaction was performed in pentane. The chloride and bromide analogues have been stucturally characterized. Attempts to isolate thetrimethylsilylmethyl complexes (rl5-C9H7)Ti(CH2SiMe3)X2 (X = Cl and Br) as puremonoalkyl species were also successful, albeit in low yield. This set of four compounds provides a set of monoalkyl indenyl titanium species in which there are small alkyl groups or large alkyl groups as well as different halides. These complexes may prove to be excellent catalysts for the polymerization of olefins. / Department of Chemistry

Thesis (Ph. D.)--University of Wisconsin--Madison, 1970. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

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

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144 leaves : ill., tables ; 26 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1977

Thesis (Ph.D.) -- University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1977.