Roman G. Kultyshev

Unusual Cationic Tris(Dimethylsulfide)-Substituted closo-Boranes: Preparation and Characterization of [1,7,9-(Me2S)3-B12H9] BF4 and [1,2,10-(Me2S)3-B10H7] BF4

Rational syntheses of trisubstituted sulfur-bearing closo-boranes are presented. In the development of these syntheses unusual cationic closo-boranes [1,7,9-(Me(2)S)(3)-B(12)H(9)](+) (3) and [1,2,10-(Me(2)S)(3)-B(10)H(7)](+) (4) have been identified. These were initially recognized to be intermediates in the formation of the neutral trisubstituted species 1,7-(Me(2)S)(2)-9-(MeS)-B(12)H(9) (1) and 1,10-(Me(2)S)(2)-2-(MeS)-B(10)H(7) (2), respectively. Stable tetrafluoroborate salts were prepared and isolated, and their structures are presented. They are believed to represent the first structural determinations of cationic borane clusters of any type.

Syntheses and chemistry of bis- and tris- mercaptoborates*

The preparation and chemistry of bis- and tris-mercaptoborates based on closo-B12 and closo-B10 structures is described. These species undergo a number of reactions such as halogenation and alkylation without changing the closo-borane core. Addition of the third dimethylsulfide substituent to the closo-boranes is thought to proceed via an unusual cationic intermediate.

CCDC 211944: Experimental Crystal Structure Determination

Related Article: R.G.Kultyshev, Shengming Liu, Hoitung T.Leung, Jianping Liu, S.G.Shore|2003|Inorg.Chem.|42|3199|doi:10.1021/ic020600u