酸诱导的[closo-B10H10]2-开环反应作为一种新途径用于制备 6-取代的 nido-B10H13 方硼烷及相关的硼烷衍生物。

Acid-induced opening of [closo-B10H10]2- as a new route to 6-substituted nido-B10H13 decaboranes and related carboranes.

机构信息

International Institute of Nano & Molecular Medicine, School of Medicine, University of Missouri, 1514 Research Park Drive, Columbia, Missouri 65211, USA.

出版信息

Inorg Chem. 2012 Sep 17;51(18):9935-42. doi: 10.1021/ic3014267. Epub 2012 Aug 27.

DOI:10.1021/ic3014267

PMID:22924628

Abstract

Protonation of the polyhedral anion closo-B(10)H(10) under superacidic conditions apparently generates an electrophilic intermediate, B(10)H(13), that forms 6-R-nido-B(10)H(13) (R = aryl, alkyl, triflate) derivatives by electrophilic aromatic substitution, C-H bond activation, or ion-pair collapse, respectively. The proposed mechanism of formation of the 6-R-nido-B(10)H(13) derivatives via the boranocation B(10)H(13) is discussed. The synthesis of carboranes, starting from 6-R-nido-B(10)H(13) decaboranes, and single-crystal X-ray diffraction analyses of several 6-R-nido-B(10)H(13) decaboranes and carboranes are described.

摘要

在超强酸条件下，多面体阴离子[closo-B(10)H(10)]的质子化显然会生成亲电中间体[B(10)H(13)]+，它分别通过亲电芳香取代、C-H 键活化或离子对坍塌形成 6-R-nido-B(10)H(13)（R = 芳基、烷基、三氟甲磺酸酯）衍生物。讨论了通过硼阳离子[B(10)H(13)]+形成 6-R-nido-B(10)H(13)衍生物的形成机制。描述了从 6-R-nido-B(10)H(13)十硼烷开始合成碳硼烷，以及几个 6-R-nido-B(10)H(13)十硼烷和碳硼烷的单晶 X 射线衍射分析。