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This dissertation consists of two independent topics: (1) a molecular loop with interstitial channels in a chiral environment; (2) study of formation of metal-metal bonds in dinickel, dipalladium and dititanium complexes On the first topic, a study of the reaction products of the interaction of cis- Mo2(DAniF)2(CH3CN)4 2+ corner pieces with ortho-, meta- and para- isomers of enatiomerically pure –O2CCH(CH3)C6H4CH(CH3)CO2 – dicarboxylate was performed. First, an enantiomerically pure molecular loop based on two dimolybdenum units and two para-dic arboxylate linkers was synthesized and structurally characterized. Similar reactions with isomeric ortho- and meta- dicarboxylate linkers, as well as with some nonchiral ligands, showed that the structure of the obtained products depends on the geometry of the ligand. Meta- dicarboxylate linker favors the formation of the chelated product and ortho- dicarboxylate linker produces the mixture of chelated molecules and loops. On the second topic, an investigation of the formation of metal-metal bonds was performed. Study of the one-electron bond obtained upon oxidation of Ni2 4+ and Pd2 4+ to Ni2 5+ and Pd2 5+, respectively, was made. The compounds synthesized were studied with various physical methods, such as X-ray crystallography, UV-visible spectroscopy and EPR spectroscopy. The nature of oxidized species as well as the dependence of metalmetal interactions on electron-donating abilities of bridging ligands was studied. It was shown that oxidation takes place on a metal center. The formation of one-electron bond in oxidized species is proposed. Finally formation of Ti2 6+ single bonded compounds by the reduction of two Ti4+ monomers to Ti2 6+ dimer was studied. The nature of the species obtained in solution and in solid state is discussed. The crystal structure shows the presence of two types of hpp ligands – chelating and bridging. NMR study of this compound in solution proposes the rearrangement of this structure to a paddlewheel.

Thesis (M.F.A.)--Rochester Institute of Technology, 1990. / Typescript. Includes bibliographical references (leaves 24-25).

Thesis (M.S.)--University of Wisconsin--Madison, 1969. / eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (Ph. D.)--University of Hong Kong, 1993.

Thesis (M.S. in mechanical engineering)--Washington State University, December 2006. / Includes bibliographical references (p. 102-107).

A series of bis [e] and [a] fused dibenzannulenes/cyclophanes have been synthesized for the first time using benzyne-like intermediates (annulynes). These include the dibenzannulene trans-2,9-di-t-butyl-14c, 14d-dihydro-14c-14d-dimethyldibenzo[fg,op]naphthacene 82b, and the metacyclophanedienes anti-[1,2;9,10]- dibenzo-5, 13-di-t-butyl-8,16-dimethyl[2.2]metacyclophane 82a, and anti-[1,2-b; 9,10-b]- dinaphtho-5,13-di-t-butyl-8,16-dimethyl[2.2]metacyclophane 85a. From these compounds several metal complexes including trans-{μ- [( 1,2,3,4,4a, 14b-η:8a,9,10,11,12,12a-η)-12c, 12d-dihydro-12c-12d-dimethylbenzo[ rst]pentaphene]]hexacarbonyldichromium 100, have been synthesized. Among the bis [e] fused compounds, pairs 82a/82b and 95a/95b show reversible and repeatable photo-switching properties both in solution and in the solid state. The pyrene forms 82b and 95b are characterized at low temperature and they thermally return to their cyclophane forms 82a and 95a at room temperature. A polystyrene based film of 82 shows a much better bistability required for photo-switching units. These properties make them potential candidates for optical memory units. For the similar naphtho[e] fused compound 95a, no pyrene isomer 95b was detected upon irradiation with UV light. Based on the NMR data, relative bond fixing abilities (RBFA) of several species are measured. The order is: [special characters omitted] > Benzene > Oxanorbomadiene > lU Norbomadiene The reduced species, oxanorbomene and norbomene, do not induce any significant bond localization on the [14] annulene ring. / Graduate

M.Sc. (Chemistry) / Please refer to full text to view abstract

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published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy