Asok Nayanthara, Gaffen Joshua R, Pradhan Ekadashi, Zeng Tao, Baumgartner Thomas
Department of Chemistry, York University, 4700 Keele Street, Toronto, ON M3J 1P3, Canada.
Dalton Trans. 2021 Feb 14;50(6):2243-2252. doi: 10.1039/d1dt00062d. Epub 2021 Jan 27.
A series of neutral pentacoordinate dithieno[3,2-b:2',3'-d]phosphole compounds were synthesized by [4 + 1] cycloaddition with o-quinones. Counter to the expected trigonal bipyramidal geometry, the luminescent hypervalent dithienophospholes exhibit square pyramidal geometry with inherently Lewis acidic phosphorus center that is stabilized via supramolecular π-stacking interactions in the solid state and in solution. Due to their Lewis-acid character, the compounds react with nucleophiles, suggesting their potential as mediator in organic transformations. The new species thus present an intriguing structural plaform for the design of neutral P(v) Lewis acids with useful reactivities.
通过与邻醌的[4 + 1]环加成反应合成了一系列中性五配位二噻吩并[3,2 - b:2',3'-d]磷杂环戊烯化合物。与预期的三角双锥几何构型相反，发光的高价二噻吩磷杂环戊烯呈现出四方锥几何构型，其具有固有的路易斯酸性磷中心，该中心通过固态和溶液中的超分子π-堆积相互作用得以稳定。由于它们的路易斯酸性质，这些化合物与亲核试剂反应，表明它们在有机转化中作为介质的潜力。因此，这些新物种为设计具有有用反应活性的中性P(v)路易斯酸提供了一个有趣的结构平台。
