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Please use this identifier to cite or link to this item: http://hdl.handle.net/1993/1884

Title: Reaction mechanisms of main group fluorinated compounds, application of the coordination model of reaction mechanisms
Authors: Ou, Xiaobo
Issue Date: 1-Jul-1998
Abstract: The Coordination Model of Reaction Mechanisms (Janzen & Jang, Can. J. Chem. 67, 71, 1989) is a topological description of the connectivity of atoms in multi-step reaction pathways which utilises directed graphs P(X,C) in which the vertex set X consists of reactants, intermediates and products, and the edge set C consists of coordination number operators +C, -C, +Cc and -Cc. This Model provides a unified description of reaction mechanisms, and it has been tested and applied successfully in the following areas: '1'. Kinetic simulations of pathways P(X,C) and comparison of the results with extensive experimental data that are available for the reaction of boron trifluoride with Lewis bases. The mechanism of reaction of boron trifluoride with amines, dialkyl ethers, and pyridine has been analyzed on the basis of the Coordination Model of Reaction Mechanisms. '2'. Molecular orbital study of silicon-fluorine and silicon-carbon bond cleavage in organofluorosificates. The mechanism of silicon-fluorine and silicon-carbon bond cleavage in organofluorosilanes and -silicates with four-, five-, and six-coordinate silicon species is analysed with the aid of molecular orbital calculations. Reaction mechanisms of phosphorus fluorides are also analysed on the basis of the Coordination Model of Reaction Mechanisms. Some of the intermediates and mechanistic details arising out of such an analysis have been investigated by 'ab initio' molecular orbital calculations. '3'. Oxidative fluorination of diphenyl sulfoxide and fluorine exchange in the Ph2S(O)F2-Ph2S(O)F + system. Oxidative fluorination of diphenyl sulfoxide with xenon difluoride occurs under mild conditions in the presence of a catalytic amount of chloride ion to give Ph2S(O)F2 in essentially quantitative yield. '4'. Oxidative addition and isomerization reactions as illustrated by the synthesis of 'cis'- and 'trans'-ArSF 4CI (Ar=Ph, 'p'-MeC6H4, ' p'-O2NC6H4) and 'cis'- and 'trans'-PhTeF4Cl. The stereoselective synthesis and isomerization of 'cis'- and 'trans'-ArSF 4Cl (Ar=Ph, 'p'-MeC6H4, ' p'-O2NC6H4) is described, and this method has also been extended to the synthesis of 'cis'- and ' trans'-PhTeF4Cl. '5'. Syntheses and isomerizations of 'cis'- and 'trans'-Ph2SF4, and syntheses of PhEF5 (E=S, Se, Te). The synthesis and isomerization of ' cis'-Ph2SF4 and 'trans'-Ph 2SF4 has been investigated, and the results are comparable to the synthesis of 'cis'- and 'trans'-Ph 2TeF4. (Abstract shortened by UMI.)
URI: http://hdl.handle.net/1993/1884
Appears in Collection(s):FGS - Electronic Theses & Dissertations (Public)

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