| The thesis consists of six parts as follows: Part I: ReviewsThis part reviewed the catalytic oxidation of alcohols including non-metal-catalyzed oxidation and metal-catalyzed oxidation, In the first section, the applications of TEMPO and its derivatives in homogeneous as well as in heterogeneous conditions in the catalytic oxidation of alcohols were well discussed. As for the metal-catalyzed oxidation, the mechanisms of the oxidation o f alcohols, and the methods for the optimizing of the oxidation were suggested. Then the author reviewed the metal-catalyzed oxidation particularly from the following ten subsections, such as (i) ruthenium complex catalyzed system; (ii) palladium complex catalyzed system (iii) chromium and its oxide catalyzed system; (iv) copper (I) complex catalyzed system; (v) manganese complex catalyzed system; (vi) iron complex catalyzed system; (vii) cobalt complex catalyzed system; (viii) osmium and the co-metal catalyzed system; (ix) double metals catalyzed system; (x) other transition metal catalyzed system, and a short conclusion was also proposed based on all of the reviews.Part II: Synthesis and characterizations of the catalystsFive 1 ow molecular weight ruthenium-containing complexes such as Phen-Ru-Phen, Phen-Ru-Quin, Phen-Ru-Bipy, Quin-Ru-Bipy and Quin-Ru-Quin were synthesized. Another polymer supported Ru(III) complexes, PS-Phen-Ru, were also synthesized w ith t he s upporter o f c hloromethyl p olystyrene r esin. The PS-Phen-Ru complexes were then modified with low molecular weight ligands such as 8-hydroquiniline, 2,2'-bipyridine and 1,10-phenanthroline to form the resulting supported catalysts named PS-Phen-Ru-Quin, PS-Phen-Ru-Bipy and PS-Phen-Ru-Phen. Furthermore, two kinds of palygorskite supported catalysts Ru/PLS and Pd/PLS were also synthesized based on the inorganic material palygorskite. All the complexes were then characterized by IR, ICP and XPS. The results show that all the catalysts were synthesized by theses methods.Part III: The catalytic properties of the low molecular weight ruthenium-containing complexes in the oxidation of alcoholsThe c atalytic a ctivities o f t he five 1 ow m olecular w eight r uthenium-containing complexes for the oxidation of benzalcohols were investigated and the optimum conditions for the oxidation were proposed respectively. Then the oxidation of other alcohols with these ruthenium-containing catalysts and PhIO under the optimum conditions w as c arried o ut a ccording to t he former r eaction c onditions. T he r esults show that all of these complexes are excellent catalysts for the oxidation of alcohols. By each of the synthesized catalysts, much of benzalcohol derivatives as well as long-chained aliphatic alcohols can be oxidized to the corresponding carbonyl compounds with high conversion (about 100% of much of alcohols) and selectivity (ca. 100%) at room temperature.Part IV: The catalytic properties of the supported PS-Phen-Ru complexes in the oxidation of alcoholsA variety of alcohols including benzylic alcohols, long-chain aliphatic alcohols, and secondary alcohols were oxidized by PhIO to the corresponding carbonyl compounds in the presence of with PS-Phen-Ru complexes according to the optimum conditions obtained from the investigation of the catalytic oxidation of benzalcohol with PS-Phen-Ru as catalysts. It is concluded that the complexes PS-Phen-Ru is another reactive catalysts for the oxidation of alcohols.Part V: The catalytic properties of the supported PS-Phen-Ru-Quin, PS-Phen-Ru-Bipy and PS-Phen-Ru-Phen complexes in the oxidation of alcoholsAll of the alcohols used in the former section were also well oxidized to the corresponding carbonyl compound by PhIO in the presence of the supported complexes PS-Phen-Ru-Quin, PS-Phen-Ru-Bipy and PS-Phen-Ru-Phen with PhIO by employing of the optimum condition obtained from the investigation of the oxidation of benzalcohol with the supported Ru(HI) catalysts, respectively. It shows that all of the three catalysts exhibit promising catalytic activities... |
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