基于碳族重元素类炔衍生物 (REER, E = Si、Ge、Sn、Pb) 成键方式及反应机理的理论研究

与线性炔烃不同，碳族重元素类炔衍生物（REER, E = Si、Ge、Sn、Pb）具有反式-弯曲的结构。基于取代基R的不同，中心E-E原子之间表现出不同的成键方式：E-E多重键和E-E单键。实验表明REER在溶液中有很高的反应活性：温和条件下可以活化H2、C2H4、C2H2、CO2、H2O、N2O等分子。其中锡炔衍生物RSnSnR可以实现对C2H4、异腈的可逆活化。对分子实现可逆活化意味着REER可以作为潜在的催化剂应用到相关领域中。我们拟用计算化学研究REER中心原子的成键方式和活化分子的反应机理，从而深入认识此类化合物的内部结构及其高活性的内在驱动力，解释实验上的困惑。在此基础上，我们将以计算化学为“实验”手段来探索新的REER化学：设计理想的电子结构和几何构型，达到对分子的可逆活化，为进一步优化设计新的活性分子/催化剂分子做准备。我们期望本课题的研究能够进一步丰富和拓展REER化学。

In contrast to the linear alkynes, the heavier group 14 element alkyne analogues (REER, E = Si、Ge、Sn、Pb) have planar trans-bent structures. On the basis of the substitutes R, REER has two different bond situations: multiply E-E and singly E-E bonded structures. Although the heavier alkyne congeners are thermally stable in the solid-state environment, they exhibit high reactivity in the solution: reacting with H2、C2H4、C2H2、CO2、H2O、N2O etc. at ambient conditions. It is worthy of mentioning that RSnSnR can perform reversible activation towards C2H4 and isocyanide, which has the potential to be used as catalyst in the related research filed. We herein use computational chemistry to deeply understand the chemistry of their chemical bonding and reaction mechanism, which can disclose the origin of their high reactivity and rationalize the experimental puzzles. Furthermore, we will use computational chemistry as ‘experimental’ tool to explore the new REER chemistry: design ideal electronic and geometric structures that can perform reversible activation toward small molecules, which can pave the way for optimizing and designing novel active molecules/catalysts. We expect that these studies will enrich the knowledge about the REER chemistry and help to develop the chemistry of group 14 elements further.