硅基低配位膦咯及其过渡金属配合物的设计、合成和应用

膦咯及其衍生物具有独特的电子结构和立体构型，广泛应用于有机太阳能电池和均相催化领域。作为配体在许多催化反应中无论是反应的选择性、还是活性都优于三苯基膦和其它有机膦配体。膦咯化学面临的挑战主要有：一是缺乏可以大量制备的方法；二是稳定性差。这严重制约着膦咯无论是作为有机分子材料，还是作为配体的应用前景。项目拟结合低聚硅烷中σ电子可以沿Si-Si键离域的特性，把低聚硅烷与膦咯通过σ结合，构建分子内含σ-π共轭效应的低配位膦咯，提高膦咯的稳定性；通过对膦咯中的氧负离子和磷原子的官能团化，制备分子内含N-P结构单元的双齿或多齿配体的低配位膦咯及其大环化合物；利用这些配体优良的配位能力和大位阻效应，调配过渡金属（Fe、Co、Ni）在催化烯丙基氯、丙炔酸酯或乙炔与三氯硅烷硅氢加成中的催化活性和区域选择性，为构建高效硅氢加成催化体系提供理论支持。

Phospholes exhibit limited aromatic character due to the inherent property of the P-atom (pyramidal geometry, inert s-pair effect), resulting in a high reactivity of both their dienic and heteroatom moieties. This behavior makes phospholes appealing derivatives for many purposes. For example, phospholes are used as organic molecular materials in organic solar cell, or as ligands in homogeneous catalysis. Thus，It is very important to explore the design, synthesis and catalytic application of the novel and stable phospholes. The main questions of phospholes are 1) there is no method for the scale synthesis of phospholes; 2) poor stability. These problems limited the develop of phospholes chemistry. In this project, a series of silicon-containing phospholes featuring σ-π conjugation effect will be prepared by applying the reaction of oligochlorosilanes with NaOCP. Owning to the bulky steric affect and σ-electron delocalization along to the Si-Si bonds of oligosilanes, the silicon-containing phospholes will be more stable. Furthermore, they will be used as building blocks for the preparation of di- or multi-dentate phosphole-containing ligands, including heteroditopic P, N-donors through the functionalization at O-anion or P atom. The coordination feature and catalytic application in hydrosilylation of phosphole-containing ligands with transition metals (Fe、Co、Ni) will also be investigate. We hope this project will support an accessible method for scale synthesis of phospholes, and a catalytic system for hydrosilylation of alkyne or alkene with trichlorosilane.