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Title: Brnsted and Lewis acid catalyzed oxidation of hydrocarbons and halide by some metal oxo, nitrido and peroxo complexes
Other Titles: Bolangsite suan he Luyisi suan cui hua jin shu han yang, han dan ji han guo yang hua he wu yang hua tan hua qing ji lu hua wu
波琅斯特酸和路易斯酸催化金屬含氧, 含氮及含過氧化合物氧化碳化氫及鹵化物
Authors: Tong, Tsz Yan (湯紫茵)
Department: Dept. of Biology and Chemistry
Degree: Master of Philosophy
Issue Date: 2004
Publisher: City University of Hong Kong
Subjects: Catalysis
Notes: CityU Call Number: QD281.O9 T66 2004
Includes bibliographical references (leaves 145-152)
Thesis (M.Phil.)--City University of Hong Kong, 2004
xvii, 152, xxii leaves : ill. ; 30 cm.
Type: Thesis
Abstract: This thesis is divided into two parts. Part I is concerned with Brønsted and Lewis acids activated oxidation of hydrocarbons by various transition metal complexes, including [OsVI(N)(salchda)Cl] (salchda = N,N’-bis(salicylidene)–trans- 1,2-diaminocyclohexane dianion), [PPh4][RuO4] and [NH4][V=O(O2)(dipic)] (dipic = dicarboxylic acid). Part II is concerned with biomimmetic halide oxidation by K2[V=O(O2)2(pic)] (pic = picolinato acid), [NH4][V=O(O2)2(phen)] (phen = 1, 10-phenthroline) and [nPr4N][RuO4]. In Part I, it was found that the oxidation various alkanes and alcohols can be catalyzed by [OsVI(N)(salchda)Cl] effectively at room temperature in the presence of a Lewis acid, using H2O2 as the terminal oxidant. Similarly, alkanes can be oxidized by [PPh4][RuO4] and [NH4][V=O(O2)(dipic)] upon addition of a few equivalents of a Lewis acid. For [OsVI(N)(salchda)Cl]/H2O2/FeCl3, [PPh4][RuO4]/FeCl3 and [NH4][V=O(O2)(dipic)]/FeCl3, the C2/C3 ratios for the oxidation of adamantane are 0.032, 0.026 and 0.31 respectively; while the KIE values for the competitive oxidation of cyclohexane and d12-cyclohexane are 3.6, 5.9 and 2.1 respectively. The mechanisms of the oxidation of alkanes by these systems have been proposed. In part II, some model reactions of haloperoxidases have been investigated. Haloperoxidases are enzymes that catalyze the oxidation of a halide (e.g. chloride, bromide or iodide) by hydrogen peroxide, which can result in halogenation of an organic substrate. It is found that [NH4][V=O(O2)2(phen)], K2[V=O(O2)2(pic)] and [nPr4N][RuO4] can catalyze the oxidation of bromide to bromine using H2O2, the bromine liberated then reacts with phenyl acetylenes (PhC2R, R=H, Me, Ph) and phenols to produce dibromoalkenes and bromophenols respectively. The mechanisms of these model reactions have been proposed.
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