Full Electron Delocalization across the Cluster in 1,12-bisBMes2-p-carborane Radical Anion

IF 14.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Journal of the American Chemical Society Pub Date : 2024-06-08 DOI:10.1021/jacs.4c03873

Lin Wu, Xinning Zhang, Michael Moos, Ivo Krummenacher, Maximilian Dietz, Arumugam Jayaraman, Rüdiger Bertermann, Qing Ye, Maik Finze, Michael Wenzel, Roland Mitric, Christoph Lambert*, Holger Braunschweig* and Lei Ji*,

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Abstract

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(BMes₂)-p-carborane (B₂pCab) 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 p-carborane bridge due to the overlap of carborane lowest unoccupied molecular orbital (LUMO) and the BMes₂ LUMO. Unlike dianions of other C₂B₁₀H₁₂ carboranes, which rearrange to a nido-form, two-electron reduction of B₂pCab leads to a rearrangement into a basket-shaped intermediate.

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1,12-bisBMes2-p-carborane Radical Anion 中簇间的全电子析出。

一般认为，三维（3D）硼烷与所附取代基之间的轭合作用非常弱。在本文中，我们报告了用一个电子还原 1,12-双（BMes2）-p-硼烷（B2pCab）得到的具有中心对称半四面体结构的自由基阴离子。由于碳硼烷最低未占分子轨道（LUMO）与 BMes2 LUMO 重叠，这种自由基阴离子在对碳硼烷桥上的两个硼中心之间显示出广泛的电子析出。与其他 C2B10H12 碳硼烷的二元离子重排为 nido 形不同，B2pCab 的双电子还原导致重排为篮形中间体。

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来源期刊

Journal of the American Chemical Society 化学-化学综合

CiteScore

24.40

自引率

6.00%

发文量

2398

审稿时长

1.6 months

期刊介绍： The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.