PREPARATION AND CHARACTERIZATION OF THE MIXED 1,3,2,4-DITHIADIAZOLYLIUM 1,2,3,5-DITHIADIAZOLYLIUM SALTS AND RELATED FREE-RADICALS - [M-SNSNC-C6H4-CNSSN]X AND [P-SNSNC-C6H4-CNSSN]X (X = 2+, .+ OR 2.)/

The salts [m- and [p-SNSNC-C6H4-CNSSN][AsF6]2, were prepared (in yield s exceeding 90%) by the reaction of [NCC6H4CNSSN]AsF6] with [SNS][AsF6 ] in liquid SO2 and were recrystallised as MeCN solvates. Partial and complete reduction of these dications (as the dichloride salts) led to the isolation and solid-state characterisation of the paramagnetic ra dical cations [m- and [p-SNSNC-C6H4-CNSSN] Cl and the diradicals [m- a nd [p-SNSNC-C6H4-)CNSSN2.. The crystal structure of [p-SNSNC-C6H4-CNSS N][AsF6]2.MeCN shows essentially planar SNSNC and CNSSN rings, rotated by 25.1 and 16.7-degrees respectively from the phenylene ring plane.