金属笼型N-杂环卡宾配合物的合成、结构及其对PCBs和Dioxin的催化脱卤作用

项目名称： 金属笼型N-杂环卡宾配合物的合成、结构及其对PCBs和Dioxin的催化脱卤作用

项目编号： No.21271189

项目类型： 面上项目

立项/批准年度： 2013

项目学科： 数理科学和化学

项目作者： 张丙广

作者单位： 中南民族大学

项目金额： 78万元

中文摘要： 设计合成来自Resorcinarene衍生化的半球状和申请人首次报道过的钵状笼型N-杂环卡宾前体，通过原料的选择或聚合度控制"笼子"的大小。制备这两类前体的金属N-杂环卡宾配合物，通过金属-配体的比例及辅助配体的不同控制配合物中金属的配位方式及配合物的结构。 配合物将被用于对多氯联苯和二恶英等永久性有机污染物的识别和催化脱卤反应, 考察几个方面对这些性能的影响: NHC卡宾的种类；金属的种类；辅助配体的种类；金属-笼状NHC卡宾配体的配比；空腔大小；空腔和金属中心相对位置。进一步研究催化机理，以期发现广谱的或对特定污染物具有良好脱氯催化性能的催化剂。 本项目开创性地将超分子主体化合物和N-杂环卡宾配合物结合于一体，合成对底物分子同时具备识别作用（通过笼中的空腔）和催化性能（通过金属中心）的笼型N-杂环卡宾配合物，并研究其性能。

中文关键词： 大环N-杂环卡宾；笼状配合物；多氯联苯；氢化脱氯；

英文摘要： The N-heterocyclic carbenes (NHC) and its metal complexes have grown explosively and numerous studies have been reported owing to their applications in catalyses and environment. The applicant reported the cylinder geometry N-heterocyclic carbene for the first time in 2010(Chem. Commun., 2010, 46, 4728-4730.), and its catalytic properties based on cyanosilylation of imines reactions demonstrated the size-selectivity catalytic performance. In order to conduct in-depth study on these complexes, the precursors from Resorcinarene derivative of the hemispherical and the cylinder geometry N-heterocyclic carbene were designed in this project. The size of the "cage" will be controlled through the selection of materials or the degree of polymerization. The synthesis of their metal-NHC complexes, the coordination mode and structure of the complex will be studied in detail. Complexes will be used for the identification of PCBs and dioxins and other persistent organic pollutants and catalytic dehalogenation to study several aspects of performance: the NHC carbene species; the type of metal; auxiliary types of ligands; metal - cage NHC carbene ligands of the ratio; cavity size; the relative position of the cavity and the metal center. Further study of the catalytic mechanism, and found broad-spectrum in order to have good

英文关键词： macrocyclic N-hetercyclic Carbene；Cage complex；PCBs；Hydrochloridation；