缺电子环丙烯鎓阳离子在FLP化学中作为路易斯酸。
Electron-deficient cyclopropenium cations as Lewis acids in FLP chemistry.
作者信息
Mandal Dipendu, Qu Zheng-Wang, Grimme Stefan, Stephan Douglas W
机构信息
Institute of Drug Discovery Technology, Ningbo University, Ningbo 315211, Zhejiang, China.
Department of Chemistry, University of Toronto, Toronto, 80 St. George Street, Ontario M5S 3H6, Canada.
出版信息
Chem Commun (Camb). 2023 Aug 29;59(70):10508-10511. doi: 10.1039/d3cc02684a.
Cyclopropenium cations incorporating electron deficient substituents are Lewis acidic despite the presence of π-electrons. The chloride and electron affinities are examined computationally and experimentally, respectively. These cations form classic Lewis acid-base adducts with PPh, while sterically demanding phosphines yield frustrated Lewis pairs (FLPs) which participate in FLP additions. Depending on the basicity of the phosphine used, addition to alkynes or alkyne deprotonation is observed. In either case, new C-C bonds are formed, thus extending the utility of the concept of FLP chemistry to these delocalized π-cations.
尽管存在π电子，但含有缺电子取代基的环丙烯阳离子仍具有路易斯酸性。分别通过计算和实验研究了其氯化物和电子亲和性。这些阳离子与三苯基膦形成经典的路易斯酸碱加合物，而空间位阻较大的膦则产生受阻路易斯对（FLP），其参与FLP加成反应。根据所用膦的碱性，可观察到其与炔烃的加成反应或炔烃的去质子化反应。在这两种情况下，都会形成新的碳 - 碳键，从而将FLP化学概念的应用扩展到这些离域π阳离子。
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