Oxysulfur compounds derived from disulfides: Stability and reactivity
Résumé
The physicochemical properties of the partially oxidized derivatives of disulfides are reviewed, and a comparison is made when possible between sulfur-sulfur and sulfur-oxygen-sulfur bridged compounds. After the introductory first chapter, the second part is devoted to the chemistry of the well-known thiosulfinates RS(O)SR: preparation, structure, reactivity with special attention to oxidation and free radical reactions. The third part concerns thiosulfonates RS(O)2SR and their isomers, the elusive vic-disulfoxides RS(O)S(O)R and sulfenyl sulfinates RS(O)OSR. Besides their preparation and chemistry, some comments are made on their structure, relative stability and occurrence. In the fourth chapter, the structure and stability of sulfinyl sulfones RS(O)2S(O)R and their isomers, sulfinic anhydrides RS(O)OS(O)R, are compared, and their preparation and reactivity are reviewed. The fifth part is related to RS2O4R molecules, among which only α-disulfones RS(O)2S(O)2R have been experimentally characterized, with only some scarce data on isomeric O-sulfinyl sulfonates RS(O)2OS(O)R. In the last part of this review, a correlation is made between the S-S or S-O bond lengths of these different compounds and their stability. It appears that the free radical chemistry of some of these molecules is necessary to account for the described reactivity data.