RAMAN-SPECTRA OF SOME COMPLEXES CONTAINING METHYLDIHALO-SULFONIUM AND DIMETHYLHALO-SULFONIUM CATIONS - ISOMERISM IN THE DIMETHYL SULFIDE BROMINE COMPLEX

被引:11
作者
ASKEW, HF [1 ]
GATES, PN [1 ]
MUIR, AS [1 ]
机构
[1] UNIV LONDON,ROYAL HOLLOWAY & BEDFORD NEW COLL,DEPT CHEM,EGHAM HILL,EGHAM TW20 0EX,SURREY,ENGLAND
关键词
D O I
10.1002/jrs.1250220506
中图分类号
O433 [光谱学];
学科分类号
0703 ; 070302 ;
摘要
Vibrational assignments for the skeletal modes of some complexes containing CH3SX2+ and (CH3)2SX+ (X = Cl, Br) have been made on the basis of their solid-state Raman spectra and compared with any previous data. The stabilities of the parent CH3SX3 and (CH3)2SX2 compounds are discussed; two isomers of (CH3)2SBr2 were obtained under varying reaction conditions and assigned as ionic [(CH3)2SBr+Br-] and charge-transfer [(CH3)2S --> Br2] 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 (CH3)2SBr+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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页码:265 / 274
页数:10
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