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This thesis described investigations into the synthesis and reactions of chiral monophosphines, in five chapters. Chapter 1 introduces asymmetric catalysis, Chapter 2 and 3 describe the synthesis of enantiomerically pure monophosphine via an oxide and borane route respectively. Chapter 4 describes the organometallic reactions of these monophosphines and Chapter 5 contains experimental details of the reactions. <strong>Chapter 1</strong> describes the importance of chirality and significant asymmetric processes. The literature methods of producing homochiral monophosphines are detailed. <strong>Chapter 2</strong> describes the synthesis of enantiomerically enriched monophosphine oxides. Diastereomerically pure (2R, 4S, 5R)-2-chloro-5-phenyl-3,4-dimethyl-1,3,2-oxazaphospholidine was prepared from PCl₃ and (-)-ephedrine. This compound was reacted with 2-adamantyl magnesium bromide to afford (2R, 4S, 5R) and (2S, 4S, 5R)-3,4-dimethyl-2-2-adamantyl-5-phenyl-1,3,2-oxazaphospholidin-2-oxide after oxidation with ^tBuOOH. An X-ray crystal structure was obtained of the R_P diastereoisomer and a detailed NMR study carried out on the S_P diastereoisomer. The R_P diastereoisomer was reacted with 2-methoxyphenylmagnesium bromide to give R_P-N-methyl-N-(1S,2S)-(1-methyl-2-hydroxy-2-phenyl)-ethyl-P-(2-methoxyphenyl)-P-(2-adamantyl)phosphinamide in 68% yield and 95% d.e. The ephedrinyl residue was replaced by O-methyl under acid catalysis with inversion of configuration and with >85% e.e. Displacement of the methoxy group using phenyl lithium occurred with inversion of configuration to give the corresponding phosphine oxide in 65% e.e., which could be reduced under forcing conditions using polymethylhydrosiloxane in the presence of Ti(OⁱPr)₄. <strong>Chapter 3</strong> describes the synthesis of enantiomerically enriched monophosphines via phosphine borane complexes. Diastereomerically pure (2R, 4S, 5R)-2,5-diphenyl-3,4-dimethyl-1,3,2-oxazaphospholidine borane was prepared directly from PhPCl₂ and (-)-ephedrine, followed by oxidation with BH₃.Me₂S. This compound reacted regiospecifically with ortho-anisyl lithium to afford the product formed by P-O cleavage with >96% d.e. and with retention of configuration at phosphorus. The ephedrinyl residue was replaced by O-methyl under acid conditions with inversion of configuration and with >98% e.e. Ferrocenyl, 1-adamantyl and tert-butyl lithium reagents displaced the methoxy group with inversion of configuration and with >92% e.e., as determined by ¹H NMR methods. The phosphine borane complexes were then reduced quantitatively with Et₂NH with retention of configuration and with >98% e.e. <strong>Chapter 4</strong> describes the synthesis of indium and rhodium complexes of (S)-t-butyl-(2-methoxyphenyl)-phenyl phosphine and (S)-ferrocenyl-(2-methoxyphenyl)-phenyl phosphine. The iridium complexes are shown to reduce a range of prochiral olefins, including Z-methyl-2-acetylamino-3-phenylpropenoate (MAC) in up to 19% e.e. The di-(R,R)-(ferrocenyl-(2-methoxyphenyl)-phenyl phosphine) rhodium complex is more selective, reducing MAC in 54% e.e., while the rhodium complex of (S)-t-butyl-(2-methoxyphenyl)-phenyl phosphine reduces MAC in 24% e.e.

Copies of author's previously published articles inserted. / Includes bibliographical references (leaves 193-215) / xiv, 216 leaves : ill. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Studies the structure and reactivity of organic, organosilicon and organophosphorus anions in the gas phase. Theoretical ab initio calculations and collisional activation in a reverse geometry mass spectrometer revealed structural information and reactivity was probed using the flowing afterglow reactor. / Thesis (Ph.D.)--University of Adelaide, Dept. of Organic Chemistry, 1991

Thesis (Ph. D.)--University of Nevada, Reno, 2006. / "May, 2006." Includes bibliographical references. Online version available on the World Wide Web.

Thesis (M.Sc. (Forensic Science))--Mahidol University, 1979.

Thesis (Ph. D.)--University of Washington, 1999. / Vita. Includes bibliographical references (leaves 83-102).

Thesis (Ph.D.) in Chemistry--University of Maine, 2003. / Includes vita. Includes bibliographical references (leaves 138-149 ).

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The study of rapid cleavage of organophosphate esters by metal ions is of great interest as it is the most important reaction in both biological and environmental sciences. A good understanding of organophosphate hydrolysis by metal ions is important as it can be exploited in formulation of useful detoxifying agents for organophosphate contaminants in the environment. The knowledge can also help in developing effective artificial enzymes. The hydrolysis of 4-NPP in the presence of Ferrous and Ferric ions in o/w microemulsion media was investigated. The reaction was monitored by measuring the absorbance of the 4-nitrophenolate ion produced in the reaction aliquots with time. The order of effectiveness of the ME media towards the hydrolysis of 4-NPP was found to be CME > AME > aqueous in the presence of Fe(II), Fe(III) and Prussian blue at neutral pH. In comparison with individual metal ions used in the investigation, it was found that polymetallic Prussian blue showed enhanced rate of hydrolysis. The degree of effectiveness is as follows; Prussian blue (insoluble) > Prussian blue (soluble) > Fe(III) > Fe(II). The result of the present investigation enriches our understanding of the possible roles polymetallic ions play in hydrolysis reactions and the effect of different reaction media. The reactions mimic the roles of purple acid phosphatases in the hydrolysis of phosphate esters. The application of the above systems for environmental decontamination of organophosphates is also envisaged. / Chemistry / M.Sc.(Chemistry)

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