The complexes Cp(,2)M(SH)(,2), where M = Ti and Zr, have been prepared and treated with S(,8) and >N-S(,x)-NN = benzimidazolyl, phthalimidyl and x = 1, 2, to give the metallacyclohexasulfanes Cp(,2)MS(,5). Reaction of Cp(,2)TI(SH)(,2) with >N-SR, where >N = phthalimidyl, succinimidyl, gave the complexes Cp(,2)Ti(S(,2)R)(,2) (R = CHMe(,2)) and Cp(,2)Ti(SR)(S(,3)R) (R = Ph, 4-C(,6)H(,4)Me). The thiolates Cp(,2)Ti(Cl)SR and Cp(,2)Ti(SR)(,2) (R = CHMe(,2), CMe(,3), Ph, 4-C(,6)H(,4)Me) were prepared for comparison. Treatment of the complexes Cp(,2)MCl(,2) with anhydrous solutions of Li(,2)E(,x) gave the complexes Cp(,2)ME(,5), where M = Ti, Zr, Hf and E = S, Se. The compounds (RCp)(,2)TiS(,5) (R = Me, SiMe(,3)),CH(,2)Cp(,2)TiS(,5), and (Me(,5)Cp)CpTiS(,5) were prepared similarly. Reaction of Li(,2)S(,x) with (Me(,5)Cp)(,2)MCl(,2) gave the metallacyclotetrasulfanes (Me(,5)Cp)(,2)MS(,3). The complex Cp(,2)Ti{S(CH(,2))(,3)S} was synthesized. Variable temperature ('1)H NMR studies established the barriers ((DELTA)G('(NOT=))) for ME(,x) and TiS(,2)C(,3) ring reversal in the above complexes. The crystal structures of Cp(,2)Ti(SPh)(S(,3)Ph), Cp(,2)MS(,5), and (Me(,5)Cp)(,2)TiS(,3) are discussed.

The last chapter describes an extension of this cyclisation reaction enabling the synthesis of homochiral l-aryl-l,2,4,5-tetrahydrobenzazepines. The stereoselectivity observed in the acid-mediated cyclisation of homochiral N-(3,4-dimethoxyphenethyl)halostachine to Nmethyl- l-phenyl-l,2,4,5-tetrahydrobenzazepine is assessed. The chromium tricarbonyl complex of this cyclisation precursor undergoes a stereoselective cyclisation to furnish the homochiral 1-aryl benzazepine after decomplexation. The diastereoselectivity observed in the acid-mediated cyclisation of homochiral N-3,4-dimethoxyphenethyl phenylpropanolamines is also investigated and the mechanism by which they occur is discussed. Coordination of one of these precursors to the chromium tricarbonyl unit renders the cyclisation stereoselective to give homochiral N-methyl-1 -phenyl-2-methyl-7,8-dimethoxy-1,2,4,5-tetrahydrobenzazepine after decomplexation.

Summary in end pocket / iv, 176 leaves : diags., graphs ; 30 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, 1978

Typescript (photocopy) / 277 leaves : ill. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.) Dept. of Physical and Inorganic Chemistry, University of Adelaide, 1982

Typescript (photocopy) / 277 leaves : ill. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.) Dept. of Physical and Inorganic Chemistry, University of Adelaide, 1982

Thesis (Ph. D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1985. / Offprints of two author's journal articles inserted at end of the v. Includes bibliographical references (leaves 10-12).

Thesis (Ph. D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1986. / Includes bibliographical references.

Thesis (M.S.)--University of Toledo, 2007. / Typescript. "Submitted as partial fulfillment of the requirements for the Master of Science Degree in Chemistry." "A thesis entitled"--at head of title. Bibliography: leaves 99-101.

Thesis (Ph.D.) Dept. of Physical and Inorganic Chemistry, University of Adelaide, 1982. / Typescript (photocopy).

Thesis (Ph.D.) -- University of Adelaide, Department of Physical and Inorganic Chemistry, 1978. / Summary in end pocket.