C-S键断裂合成高核金属团簇及其催化应用

项目名称： C-S键断裂合成高核金属团簇及其催化应用

项目编号： No.21471108

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 无机化学

项目作者： 李红喜

作者单位： 苏州大学

项目金额： 85万元

中文摘要： CS2与胺、醇、硫醇等反应生成二硫代甲酸盐类配体，使C=S键弱化、易断裂；二硫代甲酸盐类配体与铜、银、金等金属盐消除反应得到二硫代甲酸金属配合物；通过二硫代甲酸金属配合物在有机溶剂中反应，或二硫代甲酸盐配体与金属盐在有机溶剂中直接反应，发生C-S键断裂，原位合成高核金属团簇。调控二硫代甲酸盐的种类及其取代基，合成不同核数的金属团簇。测定反应溶液中C-S键断裂所形成的其它无机或有机物种，提出可能的C-S键断裂和团簇的形成机理。考察它们催化C-N/C-C键形成反应、内酯开环聚合、醇的氧化、烷基或芳基丙炔酸的脱羧偶联反应等活性，研究团簇结构对催化性能的影响。

中文关键词： C-S键断裂；团簇；合成；高核；催化

英文摘要： Reactions of CS2 with amines, or alcohols, or thiols result in the formation of dithioformate ligands, weakening the C=S bond to be cleaved easily. Reactions of these dithioformate ligands with transition metal salts produce the corresponding dithiformate transition metal coordination complexes. Reactions of the above coordination complexes in organic solvents, or direct reactions of tranistion metal salts with dithiformate ligands in organic solvents yield highnuclear clusters via the C-S bond cleavage. The structures of clusters will be adjusted through the changing the species of dithioformate ligands and the substituted groups on the ligands. Some new inorganic and organic species are seperated from the reaction solution. Based on the all results, the possible reaction mechanism of the C-S bond cleavage and the cluster formation will be proposed. We will explore the catalytic properties on the formation of C-N/C-C bonds, the ring open polymerization of lactone, oxidation of alcohols and decarboxylative coupling of aryl or alky propiolic acids of the resulting clusters. The relationship between the structures of clusters and the catalytic efficiency will be discussed.

英文关键词： C-S bond cleavage;Cluster;Synthesis;high-nuclearity;Catalysis