低价钒杂环丙烯化合物的合成、结构及反应性研究

Metallacyclopropenes have received widespread attention due to their unique structural properties and their potential applications in organic synthesis and small-molecule activation. Nevertheless, while the reactivity and properties of high-valent main group, transition and actinide metallacycles are well established and understood, the low-valent metallacycles have remained largely neglected and therefore their intrinsic reactivity remained virtually unexplored. Thus, the development of low-valent metallacycles remains a desirable and challenging goal, which is not only in academic study but also in industry.. A series of low-valent vanadium metallacyclopropene complexes would be designed and prepared, and their reactivity in small-molecule activation would be studied. The electron interaction between the vanadium ion and alkynyl ligand would be investigated by magnetic susceptibility studies, and their reactivity would be further explored by computational studies. Thus, a relationship between the electronic structure and the reactivity would be established, which would provide a theoretical basis for their potential application in organic synthesis，pharmaceutical chemicals, and energy materials. For comparsion, the vanadium metallacyles, derived from asymmetric alkyne, would also be included in this proposal.

金属杂环丙烯化合物因其独特的结构特性，在有机合成、小分子活化等领域展现了广阔的应用前景，从而获得了人们的广泛关注。但这些研究工作主要集中在高价态的主族金属、过渡金属和锕系金属。到目前为止，对低价金属杂环化合物的研究工作还处于起步阶段。因此，研究低价金属杂环化合物的合成、性质与反应，无疑具有重要的学术意义和潜在的应用价值。. 本项目拟设计并合成出一系列低价钒杂环丙烯化合物，并将其应用于小分子的活化反应，进行反应性能测试。通过磁性研究揭示其金属离子与炔烃配体之间的电子作用关系，并将结合理论计算，探讨其反应性能，研究其电子结构与反应性能之间的关系，为这类化合物在有机合成、医药化工以及能源材料方面的潜在应用提供理论依据。同时，本项目也将在不对称炔烃衍生的钒杂环化合物方面做部分研究工作，进一步探讨炔烃配体的空间效应、电子效应对钒杂环丙烯化合物的合成和反应性的影响。

低价金属有机化合物因其独特的反应性能在惰性小分子活化和合成化学领域表现出了广阔的应用前景，从而成为了金属有机化学的前沿研究课题。因此设计合成新型低价金属络合物，并研究它们的反应性能无疑具有重要的科学意义和潜在的应用价值。本项目设计合成了苯环桥联一价钒化合物和IIIA族金属络合物，并研究了它们的反应性能。研究发现，苯环桥联的反三明治结构低价（一价）钒化合物不仅可与偶氮化合物作用发生多电子转移反应，还可以通过单电子转移路径催化高价碘与烯烃反应生成一系列含季碳中心的五元环吲哚酮化合物和六元环异喹啉二酮化合物。羰基铼可以有效催化丙烯酰胺化合物的分子内环化反应。含C=N双键的1,5-苯并硫氮杂䓬化合物对白色念珠菌、金黄色葡萄球菌、白色葡萄球菌有良好的抑制作用。在本项目资金的资助下发表论文3篇，其中 Org. Chem. Front (1篇)， Dalton Trans (1篇)。另有一篇论文刚刚被接收（Molecular Catalysis, 2022, just accepted）