Wu Lin, Zhang Xinning, Moos Michael, Krummenacher Ivo, Dietz Maximilian, Jayaraman Arumugam, Bertermann Rüdiger, Ye Qing, Finze Maik, Wenzel Michael, Mitric Roland, Lambert Christoph, Braunschweig Holger, Ji Lei
Frontiers Science Center for Flexible Electronics (FSCFE), Shaanxi Institute of Flexible Electronics (SIFE) & Shaanxi Institute of Biomedical Materials and Engineering (SIBME), Northwestern Polytechnical University (NPU), 127 West Youyi Road, Xi'an 710072, China.
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
J Am Chem Soc. 2024 Jul 3;146(26):17956-17963. doi: 10.1021/jacs.4c03873. Epub 2024 Jun 8.
Conjugation between three-dimensional (3D) carboranes and the attached substituents is commonly believed to be very weak. In this paper, we report that reducing 1,12-bis(BMes)--carborane () with one electron gives a radical anion with a centrosymmetric semiquinoidal structure. This radical anion shows extensive electron delocalization between the two boron centers over the -carborane bridge due to the overlap of carborane lowest unoccupied molecular orbital (LUMO) and the BMes LUMO. Unlike dianions of other CBH carboranes, which rearrange to a -form, two-electron reduction of leads to a rearrangement into a basket-shaped intermediate.
人们普遍认为三维（3D）碳硼烷与其连接的取代基之间的共轭作用非常弱。在本文中，我们报道用一个电子还原1,12-双（三甲基硼基）-碳硼烷（）会产生一种具有中心对称半醌型结构的自由基阴离子。由于碳硼烷最低未占据分子轨道（LUMO）与三甲基硼基LUMO的重叠，这种自由基阴离子在两个硼中心之间通过碳硼烷桥表现出广泛的电子离域。与其他碳硼烷的二价阴离子重排为α-形式不同，的双电子还原会重排为一种篮状中间体。
