Preparation and characterisation of the mixed 1,3,2,4-/1,2,3,5-dithiadiazolylium salts and related free radicals; [m- and [p-SNSNC–C₆H₄–CNSSN]^x(x= 2+, ·+ or 2·)

Abstract

The salts [m- and [p-[graphic omitted]–C6H4–[graphic omitted]][AsF6]2 were prepared (in yields exceeding 90%) by the reaction of [NCC6H4[graphic omitted]][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 radical cations [m- and [p-[graphic omitted]–C6H4–[graphic omitted]]Cl and the diradicals [m- and [p-[graphic omitted]–C6H4–)[graphic omitted]2·. The crystal structure of [p-[graphic omitted]–C6H4–[graphic omitted]][AsF6]2·MeCN shows essentially planar [graphic omitted] and [graphic omitted] rings, rotated by 25.1 and 16.7° respectively from the phenylene ring plane.