The oxidation of olefins by transition metal complexes leading to epoxide or ketonic products has been reviewed, with an emphasis on non-free radical processes. The formation of cycloadducts by reaction of <u>bis</u> (triphenylphosphine )- platinum(O)dioxygen with the α,β-unsaturated carbonyl compounds <u>trans</u> but-2-enal, propenal, cyclohex-2-en-1-one, <u>exo</u> 2-methvlenecyclohexan-1-one and 3-phenylprop- 2-enal was investigated by H- and ³¹P- nuclear magnetic resonance (n.m.r.). The cycloadducts derived from <u>trans</u> but-2-enal and propenal were thermally unstable in solution and further reacted to form stable, isolable complexes. The mechanism by which the cycloadduct <u>cis</u> [4-<u>trans</u>(prop-2-enyl )-1,1-bis( triphenyl - phosphine)platina-2,3» 5-trioxacyclopentane] , I , was transformed into <u>cis</u> [<u>trans</u>- (5-formyl-4-methyl)-1,1-bis(triphenylphosphine )platina-2 t 3-dioxacyclopentane] , II , was investigated by H- and H-n.m.r. utilising <u>trans</u> 4-[²H₃]but-2-enal. A mechanism which involved both exchange of free <u>trans</u> but-2-enal with I and reaction to give II was proposed; a computer model, based upon numerical integration of the alternative rate equations was in good agreement with this proposition. The chemical reactivity of II with a variety of reagents was explored. In particular, the reaction of II with trifluoroacetic acid gave <u>trans</u> 2-formyl- 3-methyloxirane in high yield and stereoselectivity. The dynamic behaviour of <u>cis</u>[<i>bis</u>(triphenylphosphine)(2₃,3'-m)(<u>trans</u> - but-2-enal )platinum(0)] was observed by variable temperature P-n.m.r. and explained by the interconversion of carbonyl rotamers. The preparation of iridium(I) olefin and peroxo complexes has been described Chloro<u>bis</u> triphenylphosphine) (1,2-m) (ethene )dioxygen iridium( I) , III , and related complexes were found to oxidise terminal olefins to their methyl ketones stoichiometrically, by a non-free radical process. The mechanism has been discussed.

Typescript (Photocopy) / Includes bibliographical references / xix, 290 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, 1989

The biological significance of macrocyclic complexes has been recognized since they were first synthesized by Neil Curtis. They have the potential to play a critical role in mimicking metalloprotein active sites. Nine Curtis macrocyclic complexes have been studied using X-ray crystallographic techniques. Their structures have been solved and comparisons of the results have been made. Biological importance is also true of the macrocyclic counterpart; side-off and end-off compartmental ligands. In some circumstances these types of ligands are more appropriate because they have extra flexibility due to their pendant arms not being fixed in place by another head-unit, like a traditional macrocycle. The synthesis of a proposed compartmental ligand; 2,2-(N,Nʼ-bis(benzimidazole-2-ylmethyl)methylamine-5,5ʼ-di-tert-butyl-3,3ʼmethanediyl-dibenzyl alcohol (Ligand 1(L1)), has been proposed and outlined. The pendant arms: bis(benzimidazole-2-ylmethyl)amine (BBIM), were successfully synthesized and characterized with 1H NMR, IR and X-ray crystallography. The head-unit: 5,5ʼ-Di-tert-butyl-2,2ʼ-dihydroxy-3,3ʼ-methanediyl-dibenzene methanol (DHTMBA), of L1 was synthesized and characterized using 1H NMR, IR and mass spectrometry. A similar head-unit; 5,5ʼ-Di-methyl-2,2ʼ-dihydroxy-3,3ʼ-methanediyl-dibenzene methanol (DHMMBA), was synthesized in an effort to shorten the synthetic time of the head-unit. This was consequently converted to the chlorine analogue; 3,3ʼ-Bis(chloromethyl)-5,5ʼ-dimethyl-2,2ʼ-methane-diyldiphenol (Cl-DHMMB), and characterized with 1H NMR, IR and X-ray crystallography. Efforts were made to synthesize Ligand 1, but due to synthetic difficulties and time restraints this proved unsuccessful. Suggestions have been made to develop this synthesis.

Thesis (Ph. D.)--University of Hong Kong, 2007.

Thesis (M.Sc.). / Written for the Dept. of Chemistry. Title from title page of PDF (viewed 2008/01/16). Includes bibliographical references.

Thesis (Ph. D.)--University of Washington, 1997. / Vita. Includes bibliographical references (leaves [135]-142).

Thesis (M.S.)--South Dakota School of Mines and Technology, Rapid City, 1976. / Vita. Includes abstract. Includes bibliographical references (leaf 29). Also issued in print.

Thesis (Ph. D.)--University of Hong Kong, 2009. / Includes bibliographical references (leaves 304-323). Also available in print.

Thesis (Ph. D.)--University of Hong Kong, 2009. / Includes bibliographical references (leaves 214-229). Also available in print.

Thesis (Ph. D.)--University of Washington, 2004. / Vita. Includes bibliographical references (leaves 152-158).