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.