Vibrational assignments for the skeletal modes of some complexes containing CH3SX2+ and (CH3),SX+ (X = C1, Br) have been made on the basis of their solid-state Raman spectra and compared with any previous data. The stabilities of the parent CH,SX, and (CH,),SX, compounds are discussed; two isomers of (CH,),SBr, were obtained under varying reaction conditions and assigned as ionic [ (CH,),SBr+Br-1 and charge-transfer [ (CH,),S + Br, I forms. The transition of the ionic (metastable) form to the more stable charge-transfer form was monitored by differential scanning calorimetry. High-frequency shifts occur in some fundamental modes of (CH,),SBr+Br-when Br-is replaced with a polyatomic anion, analogous to those seen in halophosphonium complexes; this is rationalized in terms of anion-cation interaction.
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