SIGNIFICANT INTRAMOLECULAR SULFUR-SULFUR INTERACTIONS IN CIS-2,3-DIMETHYL-5,6-DITHIABICYCLO-[2.1.1]HEXANE AND TRANS-2,3-DIMETHYL-5,6-DITHIABICYCLO-[2.1.1]HEXANE

Reduction of (+/-)-(1 alpha, 2 alpha, 3 beta, 4 alpha, 5 beta)-2,3-dim ethyl-5,6-dithiabicyclo[2.1.1]hexane 5-oxide (3a) and (1 alpha, 2 alph a, 3 alpha, 4 alpha, 5 beta)-2,3-dimethyl-5,6-dithiabicyclo[2.1.1]hexa ne 5-oxide (3b) gives the bis-sulfides -trans-2,3-dimethyl-5,6-dithiab icyclo[2.1.1]hexane (2a) and cis-2,3-dimethyl-5,6-dithiabicyclol[2.1.1 ]hexane (2b), respectively. Bis-sulfides 2a and 2b, on oxidation with one equivalent of m-CPBA give 3a and 3b, respectively, as the only pro ducts. Significant sulfur-sulfur interactions in 2a and 2b are indicat ed by the long-wavelength UV maxima, the lowered ionization potentials , as measured by photoelectron spectroscopy, and the lowered oxidation potentials, as found by cyclic voltammetry.