Practical synthesis of 9-methylthio-7,8-nido-carborane [9-MeS-7,8-C2B9H11]-. Some evidences of BH•••X hydride-halogen bonds in 9-XCH2(Me)S-7,8-C2B9H11 (X = Cl, Br, I)

被引：29

作者：

Anufriev, Sergey A. ^{[1
]}

Sivaev, Igor B. ^{[1
]}

Suponitsky, Kyrill Yu. ^{[1
]}

Bregadze, Vladimir I. ^{[1
]}

机构：

[1] Russian Acad Sci, AN Nesmeyanov Inst Organoelement Cpds, Vavilov Str 28, Moscow 119991, Russia

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2017年 / 849-850卷

基金：

俄罗斯科学基金会;

关键词：

nido-Carborane; Sulfonium derivatives; B-H center dot center dot center dot X hydride-halogen interactions; Synthesis; NMR spectroscopy; ALKALI-METAL AMIDOBORANES; REDOX CONTROL; HYDROGEN; COMPLEXES; CRYSTAL; DERIVATIVES; TRANSITION; CHEMISTRY; BIS(DICARBOLLIDES); FLUORESCENCE;

D O I：

10.1016/j.jorganchem.2017.03.025

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Convenient method of synthesis of 9-methylthio-7,8-nido-carborane [9-MeS-7,8-C2B9H11](-) based on demethylation of the dimethylsulfonium derivative 9-Me2S-7,8-C2B9H11 with sodium amide in toluene was developed. A series of alkylmethylsulfonium derivatives of nido-carborane containing heteroatoms with lone electron pairs at alpha-position of alkyl were prepared 9-XCH2(Me)S-7,8-C2B9H11 (X = Cl, Br, I, OMe) by alkylation of [9-MeS-7,8-C2B9H11](-). The B-11 NMR spectra of these compounds demonstrate splitting signals corresponding to B(5) and B(10) atoms that can be explained by the weak intramolecular B-H center dot center dot center dot X interactions in the diastereomers containing alkyl groups directed downwards and upwards relatively to the nido-carborane pentagonal face. The existence of such interactions was supported by quantum chemical calculations. (C) 2017 Elsevier B.V. All rights reserved.

引用

页码：315 / 323

页数：9

共 76 条

[11] Reactions of 1,1'-bis(diphenylphosphino)ferrocene with boranes, thiaboranes, and carboranes [J].