Thesis--University of Florida. / Description based on print version record. Typescript. Vita. Bibliography: leaves 217-226.

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published_or_final_version / Chemistry / Master / Master of Philosophy

Thesis (Ph. D.)--University of Hawaii at Manoa, 1991. / Includes bibliographical references (leaves 78-83) / Available also on microfiche / xiii, 83 p. leaves, bound ill. 29 cm

Thesis (M. Phil.)--University of Hong Kong, 1997. / Includes bibliographical references.

This study investigates the synthesis of rhenium(III)-isocyanide complexes with potentially bidentate ligands, as well as the reactivity of isocyanide ligands toward rhenium(I) and (V). The crystal structures of all the complexes have been determined by X-ray diffraction methods. The coordination behaviour of trans-[ReIIICl3(t-BuNC)(PPh3)2] with aniline and its derivatives were investigated. The isocyanide-containing rhenium(V) complexes [ReCl3(t-BuNC)(L)(PPh3)] were isolated, with the ligands H2L (aniline, o-phenylenediamine and anthranilic acid). In all these complexes the dianionic ligands L are coordinated monodentately as the imide. However, with 2-aminophenol the complexes [ReVCl2(t-BuNC)(L)(PPh3)2](ReO4) and [ReIIICl2(t-BuNC)(ibq)(PPh3)2] (ibq- = 2-iminobenzoquinonate) were identified as the products. [ReCl2(t-BuNC)(L)(PPh3)2](ReO4) is the product of a disproportionation reaction from Re(III) to Re(VII) and Re(V). All the above complexes show a distorted octahedral geometry around the rhenium. The products of the reaction of the Re(I) complex [Re(CO)5Cl] with isocyanides (tert-butyl- and cyclohexylisocyanide) are reported. Rhenium(I) tricarbonyl complexes of the form [Re(CO)3(CNR)2Cl] were isolated and they were characterized structurally and spectroscopically. The tricarbonyls are coordinated in the typical facial-fashion, whereas the isocyanides are coordinated cis to each other. The reaction of [Re(CO)3(t-BuNC)2Cl] with H2O led to the formation of the rhenium(I) complex [Re(CO)3(t-BuNC)2(OH2)] in which the aquo ligand can readily be substituted by a more complex ligand. The reaction of the rhenium(V) complexes cis-[ReO2I(PPh3)2] and mer-[ReOCl3(SMe2)(OPPh3)] with isocyanides were studied. The seven-coordinate trigonal prismatic, square faced monocapped rhenium(III) complex [ReI3(t-BuNC)3(PPh3)] was surprisingly isolated upon reacting cis-[ReO2I(PPh3)2] with tert-butyl isocyanide. The dimeric complex (μ-O)[ReOCl2(CNC6H11)2]2 was obtained from the reaction of mer-[ReOCl3(SMe2)(OPPh3)] with cyclohexyl isocyanide.

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Thesis (Ph. D.)--University of Alberta, 2009. / Title from pdf file main screen (viewed on July 16, 2009). "A thesis submitted to the Faculty of Graduate Studies and Research in partial fulfillment of the requirements for the degree of Doctor of Philosophy, Department of Chemistry, University of Alberta." Includes bibliographical references.