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Abstract

The reaction of Cs₂[B₁₀H₁₀] with DMSO in acid produces the disubstituted 1,10-, 1,6-, and 2,7(8)-isomers of (Me₂S)₂B₁₀H₈ as well as the monosubstituted [(Me₂S)B₁₀H₉]^- anion. Through a modified procedure, the trisubstituted compound 1,10-(Me₂S)₂-2-(MeS)B₁₀H₇ was prepared and characterized. The 1,10-(Me₂S)₂B₁₀H₈ isomer was converted to the enantiomers 2,7-(Me₂S)₂B₁₀H₈ and 2,8-(Me₂S)₂B₁₀H₈ which were separated on a chiral column. The 1,6-(Me₂S)₂B₁₀H₈ isomer was converted to a mixture of 1,10-(Me₂S)₂B₁₀H₈ and 2,3-(Me₂S)₂B₁₀H₈. These polyhedral rearrangements are believed to occur through the diamond-square-diamond mechanism. The 1,6- and 1,10-(Me₂S)₂B₁₀H₈ isomers were reduced with alkali metal in liquid ammonia to produce the dianions [1,6-(MeS)₂B₁₀H₈]^2- and [1,10-(MeS)₂B₁₀H₈]^2-, respectively. Sodium ethanethiolate was used for the reduction of [1-(Me₂S)B₁₀H₉]^- and 1,10-(Me₂S)₂B₁₀H₈ to form [1-(MeS)B₁₀H₉]^2- and [1-(MeS)-10-(Me₂S)B₁₀H₈]^-, respectively. The structures of 1,10-(Me₂S)₂B₁₀H₈, 1,6-(Me₂S)₂B₁₀H₈, 2,8-(Me₂S)₂B₁₀H₈, 2,3-(Me₂S)₂B₁₀H₈, 1,10-(Me₂S)₂-2-(MeS)B₁₀H₇, [1-(MeS)-10-(Me₂S)B₁₀H₈]^-, and [1,6-(MeS)₂B₁₀H₈]^2- were determined by single-crystal X-ray diffraction analysis.

Keywords: Boranes; Decaborane; Rearrangements; Reductions; Dimethyl sulfide; X-Ray diffraction; Crystal structure.

References: 28 live references.