Thesis (Ph.D.)--Virginia Commonwealth University, 2008. / Prepared for: Dept. of Anesthesiology. Title from title-page of electronic thesis. Bibliography: leaves 103-118.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1957. / Typescript. Abstracted in Dissertation abstracts, v. 17 (1957) no. 7, p. 1478-1479. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 55, 117-119).

Hexafluoroacetone readily adds to primary and secondary arsines to form arsino-1,1,1,3,3,3-hexafluoro-propanols and to tetramethyldiarsine to form a moderately stable 1:1 complex at 20° . Trimethylarsine affords a 1:1 complex with hexafluoroacetone at 0° although the complex is completely dissociated at 20°. Trimethylsilahe, trimethylgermane, and trimethyltin hydride react with hexaf luoroacetone to form 1,1,1, 3, 3, 3,-hexaf luoropropoxy derivatives and to dialkyltin dihydrides to form the bis(hexafluoropropoxy) derivatives. Addition of a second mole of hexafluoroacetone to form 1:1 complexes with propoxygermane and propoxysilane occurs at 20°in the presence of excess hexafluoroacetone. The analogous 1:1 tin complex can be isolated and is stable at 25°. Dimethylbis (1,1,1 ,3, 3, 3-hexaf luoropropoxy) tin gives a stable complex containing two moles of hexafluoroacetone. The structures of the arsine- and Group IV- hexafluoroacetone complexes and some of their reactions are discussed. The fluorocycloolefins, perfluorocyclobutene and 1,2-dichlorotetrafluorocyclobutene react with secondary arsines to give arsinocyclobutene derivatives. Perfluorocyclobutene affords the 1:1 adduct when heated with trimethylsilane and trimethylgermane. Trimethyltin hydride adds to perfluorocyclobutene at 20°to form the 1:1 adduct which subsequently slowly decomposes to trimethyltin fluoride. The reaction-of Group IV hydrides with 1, 2-dichlorotetraf luorocyclobutene affords a number of products the nature of which varies with the Group IV metal or metalloid. Thus the reaction of the dichlorocyclobutene with triethyltin hydride gives only triethyltin chloride, with trimethylsilane chlorotrimethylsilane and 1-chlorotetraf luorocyclobutyl-2-trimethylsilane are obtained,and with trimethylgermane reaction gives a variety of cyclobutenyl and cyclobutylgermanes as well as chlorotrimethylgermane. The configuration and conformation of the cyclobutyl derivatives of the Group IV elements are established from an analysis of their ¹H n.m.r. spectra. Hexafluorobut-2-yne adds quantitatively to tin hydrides at 20° to afford the 1,1,1,4,4,4-hexafluorobutenyl derivatives. Hexamethylditin, tetrakis (trifluoromethyl) diarsine, trimethylsilane and triethylgermane add to hexafluorobut-2-yne on ultraviolet irradiation to give 1:1 adducts. The 1:1 trimethylsilane-hexafluorobut-2-yne adduct also forms at 235°. Trimethyltin hydride and 1,1,1,-trifluoropropyne react slowly at 20° to afford the 1:1 adduct. A study of the isomer distribution of the 1:1 acetylene adducts indicates in all cases a predominant formation of the transisomer. Trimethylsilane catalyzes the conversion of trans-1,1,1,4,4,4-hexafluorobutenyltrimethylsilane to the cis-isomer and trimethyltin hydride catalyzes the conversion of cis-1,1,1-trifluoropropenyl-3-trimethyltin to the trans-isomer. The diadducts (CH₃) ₃SiCHCF3-CH(CF₃)Si(CH₃)₃ and ((CH₃)₃Sn)₂CHCH₂CF₃, are also obtained simultaneously with the formation of the respective 1:1 adducts although they are not formed by addition of the hydrides to the 1:1 adducts. / Science, Faculty of / Chemistry, Department of / Graduate

Organofluorine compounds are highly desirable products owing to the unique physical and chemical properties imparted by fluorine. Fluorocarbons are useful molecules that are used in multiple industries such as refrigeration, agrochemicals, pharmaceuticals, insecticides, high-value fluoropolymers and reagents in catalysis. As ligands, they are privileged in the relative inertness of the C–F bonds and their electrophilicity, which makes them ideal candidates for coordination chemistry with late, electron rich metals. Chapter 2 describes the preparation of new Ni metallacyclopentene complexes with phosphite and bis(phosphine) ligands and investigates the reaction of the latter with Lewis acidic trimethylsilyltriflate, TMSOTf (Tf = SO2CF3). As phosphine ligands react with the perfluoro-butadiene (PFB) substrate, the phosphite complex Ni((2-C4F6)[P(O-i-Pr)3]2 (2-1) was prepared from Ni(cod)2 /2 P(O-i-Pr)3 and excess PFB. Reaction of 2.1 with bis(phosphine) dppe [1,2-bis(diphenylphosphine)ethane] proceeded slowly with release of P(O-i-Pr)3 and formation of electron-rich Ni(2-C4F6)(dppe) (2-2) that undergoes fluoride abstraction using TMSOTf. The major product is proposed to be a dienyl complex resulting from ring contraction and cycloreversion. In Chapter 3 we investigate reactions of fluoroalkenes with cobalt hydrides containing phosphine and phosphite ligands in order to see if their reactivity can be controlled by the ligands’ steric and electronic properties. The four cobalt compounds used were CoH[P(OiPr)3]4 (3-1), CoH[P(O-o-tol)3]n (3-2), CoH(triphos)(CO) (3-3); [triphos = bis(diphenylphosphinoethyl)-phenylphosphine], and CoH(PPh3)3(N2) (3-4). In light of previous reports of tetrafluoroethylene insertion into Co carbonyl hydrides, we were surprised that analogous reactivity was not observed except for 3-4. Instead, reactions with hexafluoropropene gave a mixture of alkene cobalt fluoride and cobalt alkenyl complexes. In Chapter 4 we summarize our contributions to knowledge and compare our results to those from the current state of the art.

The catalytic, vapor-phase fluorination of dichloromethane to chlorofluoromethane with 38% hydrofluoric acid was investigated as a model system for possible direct utilization of hydrofluoric acid in the production of fluorocarbons and chlorofluorocarbons. Catalysts consisting of Cr or Ni supported on alumina and Ni, Cr, Ag, Co, La, Sn, Hg(I), Hg(II), Cu, Fe, Ru, Zn, Na, or Ca supported on activated charcoal were utilized at various reaction temperatures and reactor residence times. Alumina-supported catalysts were found to have low activities for fluorination in comparison to catalysts utilizing anhydrous HF reported in the patent literature. The low activities were attributed to low catalyst surface areas resulting from the fluorination of the catalyst with aqueous HF. Carbon-supported catalysts were found, in general, to promote thermal cracking of the CH2Cl2 feed as well as the fluorination reaction. This thermal cracking was usually sufficiently severe to result in drastically lowered yields of the desired product and low catalyst lifetime due to coking. The greatest selectivities for the desired product, CH2ClF, relative to the difluorinated product, CH2F2, at reasonably high conversions, were obtained with Sn, Cu, or Co fluorides on an activated charcoal support, although overall yields were relatively low due to thermal cracking.

No description available.

viii, 160 leaves : ill., tables ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1978

viii, 160 leaves : ill., tables ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1978

Thesis (M.S. - Hydrology and Water Resources)--University of Arizona, 1982. / Includes bibliographical references (leaves 73-75).

Thesis (Ph.D.)-- University of Adelaide, Dept of Physical and Inorganic Chemistry, 1978.