Synthesis of Perchlorinated Sulfonium Derivatives of -Decaborate Anion [2-BClSR] (R = -CH, -CH, -CH, -CH, -CH, -CH, CHPh, and -S(CH)).

A method for obtaining perchlorinated di-,-substituted derivatives of the -decaborate anion with various alkyl groups has been developed: [BClSR] (R= -CH, -CH, -CH, -CH, -CH, -CH, CHPh, and -S(CH)). The method is based on the preparation of the sulfonium-substituted anion [BHSR] by alkylation of the anion [BHSH] with bromoalkanes (-CHBr, -CHBr, -CHBr, -CHBr, -CHBr, -CHBr, PhCHBr, and BrCH(CH)CHBr) followed by the cluster chlorination with sulfuryl chloride SOCl in acetonitrile. The process proceeds until the hydrogen atoms in the boron cluster are completely replaced with chlorine and completes within 60 h. It has been found that the melting point of salts ((CH)N)[BClSR] (R= -CH, -CH, -CH, -CH, -CH, and -CH) strongly depends on the length of the hydrocarbon chain of the substituent R.