新型硅烯化合物的合成及其在小分子活化中的应用

项目名称： 新型硅烯化合物的合成及其在小分子活化中的应用

项目编号： No.21472032

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 李志芳

作者单位： 杭州师范大学

项目金额： 86万元

中文摘要： 一些储存化学能的小分子，如：H2、CO2、CO、NH3、N2O、N2 和CH4等在工农业生产领域有着广泛的用途。如：用作生物燃料,制备基础化工原料和合成比较复杂的有机化合物等。构建适合活化小分子化合物的催化体系一直是一项富有挑战性的工作。昂贵的过渡金属及其络合物在小分子的活化领域一直处于主导地位,而价格低廉，无毒的主族元素化合物在小分子活化领域的研究进展比较缓慢。本项目拟合成高活性的二烷基硅烯和二硅基硅烯化合物，进而与小分子化合物反应，把小分子转化为有用的较复杂的化合物，并探索其反应机制。通过研究二烷基硅烯与路易斯酸、碱形成的空间受阻型路易斯酸碱对与氢气的可逆反应，系统性地研究路易斯酸、碱的强弱，取代基空间位阻，反应压力等对反应的影响。选择高活性空间受阻型路易斯酸碱对作为催化剂，考察其在亚胺、乙腈、醛、酮和二氧化碳等官能团化合物催化加氢中的应用。

中文关键词： 主族元素；硅烯；小分子活化；氢化

英文摘要： Small molecules (H2、CO2、CO、NH3、N2O、N2 and CH4) are important compounds in industry and agriculture. They are widely used as biofuels, chemical materials and for the synthesis of complicated organic compounds. The activations of small molecules are an interesting aspect in organometallic chemistry and industry catalysis, which has attracted much attention in recent years. Until now, most of the chemical and biological systems that have been applied to the activation of small molecules are almost exclusively the domain of transition metals. Main group compounds induced small molecules activations are less studied. In this project, high reactive dialkylsilylene(15) and disilylsilylene (16 and 17) will be synthesized. Theirs activation of small molecules and the reaction mechanism will be investigated. Dialkylsilylene 15, as an amphipathic specie can form frustrated Lewis pairs （FLPs）with Lewis bases (Ph3P, Et3P, Ph3N and Et3N,) or Lewis acids (Ph3B, Et3B). These FLPs reactive toward hydrogen, and its application on the hydrogenation of imines, carbonyl compounds and carbon dioxide will be studied.

英文关键词： Main group element;Silylene;Small molecule activation;Hydrogenation