A variety of S-alkylated products was prepared by alkylation of methyl thioethers [MeSB12H11](2-)(5), [1-(MeS)-2(7,12)-(Me2S)B12H10](-) (6-8), and [1,2(7,12)-(MeS)(2)B12H10](2-) (9-11) with alkyl halides and tosylates in acetonitrile. Since these methyl thioethers can be prepared easily in B-10-enriched form on a large scale and due to their chemical versatility, they are potentially very attractive boron entities for the design and synthesis of therapeutics for boron neutron capture therapy of cancer. It was found that alkylation of 6-8 can be complicated by an equilibrium which establishes between, on the one hand, one of the former species and, on the other hand, 1,2(7,12)-(Me2S)(2)B12H10 (2-4) and [1,2(7,12)-(MeS)(2)B12H10](2-) (9-11). A boronated phosphonate 1-(MeS(CH2)(4)P(O)(OEt)(2))-7-(Me2S)B12H10 (14g) and a gem-bisphosphonate 1-(MeS(CH2)(3)CH[P(O)(OEt)(2)](2))-7-(Me2S)B12H10 (14h) were prepared from thioether 7 and the corresponding iodide and tosylate, respectively, and subsequently converted to their sodium salts. The propargyl sulfonium salts obtained by alkylation of thioethers 7, 8, 10, and 11 with propargyl bromide have been further converted to two- and three-cage oligomers containing both ortho-carborane and dodecaborane moieties. Methyl thioethers derived from closo-[B12H12](2-) are excellent participants in Michael addition reactions in the presence of a strong acid. The sulfonium salts with tertiary alkyl and vinyl substituents have been prepared by this method. Methyl thioethers 5-11 react with hyclroxylamine-O-sulfonate yielding the corresponding aminosulfonium salts, albeit in lower yields as compared to those in the alkylation reactions. Several derivatives of methyl thioethers 5-11 have been characterized by single-crystal X-ray diffraction.