面向硅烷活化的金属合金纳米晶合成和催化研究

Promised with industry applications, small molecule activation by metal alloy nanocrystals is an important topic in the inter-disciplinary research between inorganic and organic chemistry. Catalytic activation of silanes is widely implicated in material, organic and medicinal chemistry, yet confronted with prominent challenges. Through the close collaboration with Prof. Yadong Li at Tsinghua University, our earlier work has uncovered that metal nanocatalysts often show excellent catalytic properties and unique multi-center catalysis in organic reactions including silane activation. It is in this context that this proposal aims to (1)synthesize various metal alloy nanocrystals, use them as probes to study the influence of structural factors (components, composition,size,morphology and surface) on silane activation, discover novel catalysts with various activity; (2)select suitable catalysts for silane-mediated reactions, design and optimize the catalyst according to structure-property relationship so as to develop highly efficient/selective reactions and to extend the applications of metal nanocatalysts in organic transformations.

金属合金纳米晶催化的小分子活化是无机及有机化学交叉领域一个具有重要科学意义和潜在应用前景的研究方向。小分子硅烷的催化活化是材料化学，有机化学和药物化学中的一个应用广泛而具有挑战的课题。通过和清华大学李亚栋研究组紧密合作，我们在前期工作中发现了金属纳米催化剂在硅烷活化等反应上具有优异性能和独特的多中心催化行为。在此基础上，本项目拟（1）合成多种金属合金纳米晶，将它们作为探针来探索催化剂结构(如组分，组成，尺寸，形貌，表面)对硅烷活化的影响，发现具有不同活性的新催化剂；（2）根据上述结果，针对若干硅烷介导的有机反应选择适宜催化剂，通过研究构效关系来设计和优化催化剂，从而实现高效率高选择性的目标反应,拓展金属纳米催化剂在有机反应中的应用。

本项目以纳米材料合成为出发点，探索各种催化剂在硅烷活化中的反应活性，发展硅烷介导的有机新反应。取得了以下结果： (1)制备了多种纳米催化剂，包括AuAg, PdCu, PdAu, PdCo纳米晶以及纳米多孔金；(2)发现了纳米多孔金是硅烷的活化的理想催化剂，并借助纳米多孔金实现了一步法合成硅缩酮，硝基还原，炔烃半还原等反应；(3)发现了均相Rh催化剂在Si-H及Si-C键活化中的新反应性，以Rh—Si为活性中间体发展了多种新型硅烷（包括手性硅烷）的合成方法。本项目的研究结果，为硅烷活化提供了新型催化剂，为多种含硅分子的合成提供了新方法。