Thesis (Ph. D.)--University of Hong Kong, 2010. / Includes bibliographical references (leaves 242-264). Also available in print.

Thesis (Ph. D.)--University of Hong Kong, 2010. / Includes bibliographical references (leaves 242-264). Also available online.

Thesis (M.S.)--University of Wisconsin--Madison, 1964. / eContent provider-neutral record in process. Description based on print version record. Bibliography: l. 13.

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

Thesis (M.S.)--University of Wisconsin--Madison, 1967. / eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

A new compound of iodine (VII), IOF . was prepared pure in bulk quantities by the reaction of IF₇ with H₂O or SiO₂, followed by the removal of IF₇ from the resulting IF₇ /IOF₅ mixture with SbF₅ . IOF₅ was characterized by its infrared and ¹⁹F n.m.r. spectra, both of which confirmed the expected C₄v symmetry for the molecule. Since our studies indicated that previous work on IF₇ was carried out with samples containing IOF₅ , IF₇ was reinvestigated, using ¹⁹F n.m.r. and infrared spectroscopy to establish its stereochemistry. The infrared spectrum suggested a high symmetry, likely D₅h, for IF₇ while the ¹⁹F n.m.r. spectrum showed that rapid intramolecular rearrangement occurred in the liquid phase. Vapour pressure-temperature data were obtained for both IF₇ and IOF₅ ; these suggested that neither IF₇ nor IOF₅ was associated in the liquid or solid states. Some comments have been made on the acid-base behaviour of IF₇ and IOF₅ . IOF₅ shows no tendency to act as either a fluoride ion donor or acceptor, but IF₇ in addition to acting as a donor to AsF₅ and SbF₅ may show acceptor properties, previously unrecorded. The acid-base adduct IF₇ .AsF₅ was characterized by its structure, determined from X-ray powder data; and infrared spectrum as the ionic salt, IF⁺₆AsF⁻₆. The results of magnetic measurements on XeF₆ have been presented and have been suggested to be inconsistent with the hypothesis that XeF₆ is a molecule with a non-octahedral ground state and a low-lying triplet state. The reactions of ONF with the third transition series hexafluorides, and with ReF₇, ReOF₅ and OsOF₅ were studied, along with the reactions of NO with ReF₇ , ReOF₅ and ReF₆. The results confirmed the trend of increasing oxidizing power across the series from tungsten to platinum, established previously in these laboratories. The decreasing tendency to form higher coordinate anions and the variation in anion sizes across the series has been noted, and these have been shown to be consistent with the trend of oxidizing power. The reaction of ONF with IrF₆and PtF₆ has provided the first example of a fluorine elimination reaction: ONF + MF₆→NOMF₆ + F₂(+ ONF₃). The existence of fluorine as a reaction product was conclusively proven and comments on the mechanism of the reaction have been made. The ONF-PtF₆ reaction also provided the first synthetic route to the preparation of pure NO⁺PtF⁻₆. Infrared spectroscopic, magnetic susceptibility, and X-ray powder data have been given for this salt. The experimental evidence is consistent with the formulation of the compound as a derivative of platinum (v). The magnetic data for HOPtF₆, along with the data for O₂PtF₆, has been used to derive magnetic moments for the dioxygenyl cation, O⁺₂. The volumes of the O⁺₂ and NO⁺ cations have been compared. / Science, Faculty of / Chemistry, Department of / Graduate

The compound previously identified as palladium trifluoride and as such accepted as the only unambiguous tervalent palladium compound, has been shown to be the mixed valence compound Pd²⁺[PdF₆]²⁻. This has resolved difficulties associated with the description of PdF₃ in terms of crystal field theory. The synthesis of a new series of compounds of general formula Pd²⁺[MF₆]²⁻, isomorphous with Pd²⁺[PdF₆]²⁻and magnetically similar to the latter has been achieved. The oxidation state of palladium excited by bromine trifluoride has been shown to be +4 when good fluoride ion donors are available (i.e.when the solution is basic) and +2 when good fluoride ion acceptors are present in solution (i.e. in acid conditions). Reasons for the instability of Pd(III) in a fluorine ligand environment are discussed. Antiferromagnetic ordering has been observed in palladium difluoride. -This has accounted for the low value of the room temperature magnetic moment of the compound. A less tedious synthesis of palladium difluoride has been accomplished by the pyrolysis of the new palladium(II) hexafluorogermanate(IV), at temperatures above 350°. A tetrafluoride of palladium has been prepared for the first time. It is the highest valence binary palladium fluoride now known. It has a body centered tetragonal lattice and is isostructural with uranium and thorium tetrachlorides. The adduct of palladium tetrafluoride with bromine trifluoride, (BrF₃)₂PdF₄, has been prepared and was found to be isomorphic with the corresponding platinum compound. The magnetic susceptibility of gold trifluoride has been reinvestigated. Analytically pure AuF₃ has been shown to be diamagnetic. This has unambiguously assigned a low spin d⁸ configuration for Au(III) in gold trifluoride. Fluoroaurates(III) of sodium, potassium, nitrosyl, rubidium and caesium have been found to be diamagnetic. The salts with the exception of CsAuF₄ proved to be isomorphous. Also NOAuF₄ has been found to be isomorphous with NOBrF₄. The existence of a tetrapositive state of gold has been indicated. Gold tetrafluoride is a pale yellow, highly reactive solid. This first paramagnetic compound of gold is amorphous to x-rays. The previously unknown pentapositive state of rhodium has been established. Rhodium pentafluoride is a deep red solid, m.p. 95.5°, and is highly reactive. It reacts with carbon tetrachloride, chlorine monofluoride being among the products. It is structurally similar to ruthenium pentafluoride, but has a smaller molecular volume. A hexafluororhodate(V) has been prepared for the first time by reacting rhodium pentafluoride with stoichiometric amount of caesium fluoride in iodine pentafluoride. It is structurally similar to the other caesium hexafluorometallates(V) of the noble metals. The hitherto unknown iridium pentafluoride has been established and its identity with the previously known iridium tetrafluoride has been revealed. Iridium pentafluoride is structurally similar to the other noble metal pentafluorides, and is almost isodimensional with ruthenium pentafluoride. It has magnetic properties typical of a third transition series d⁴ electronic configuration in an octahedral or near octahedral environment. It is suggested that in both rhodium and iridium pentafluoride the structural unit is a fluorine bridged tetramer as in ruthenium pentafluoride. / Science, Faculty of / Chemistry, Department of / Graduate

Thesis (M. Sc.)--University of Queensland, 2003. / Includes bibliographical references.

Thesis (Ph. D.)--Indiana University School of Dentistry. / eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (M.S.)--University of Michigan, 1966.