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- W2000474756 abstract "Room temperature reactions of the rhodium and iridium bromides (η-9-SMe2-7,8-Me2-7,8-C2B9H8)MBr2 (M = Rh (1a), Ir (1b)) with CpTl give the dicarbollide thioether complexes (η-9-SMe-7,8-Me2-7,8-C2B9H8)MCp (2a,b), as a result of demethylation of the SMe2 substituent. These reactions are accompanied by transformation of cage structure from pseudocloso to closo. Refluxing of the sulfonium derivatives [(η-9-SMe2-7,8-Me2-7,8-C2B9H8)MCp]+ (3a,b) with [Bu4N]Br also affords 2a,b. In the same manner ruthenacarboranes [(η-9-SMe2-7,8-C2B9H10)Ru(η-C6H6)]+ (4a) and [(η-10-SMe2-7,8-C2B9H10)Ru(η-C6H6)]+ (4b) react with halide ions giving the thioether complexes (η-9-SMe-7,8-C2B9H10)Ru(η-C6H6) (5a) and (η-10-SMe-7,8-C2B9H10)Ru(η-C6H6) (5b). Dependence of the demethylation rate on the nature of halide ion and solvent was studied both experimentally and theoretically. The structures of 2a and 3aPF6 were determined by X-ray diffraction." @default.
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- W2000474756 date "2015-12-01" @default.
- W2000474756 modified "2023-10-17" @default.
- W2000474756 title "Demethylation of the SMe 2 substituent in cationic metallacarboranes. Halide anion influence" @default.
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- W2000474756 doi "https://doi.org/10.1016/j.jorganchem.2015.04.007" @default.
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