Electrosynthetic and other studies of sulfur imides and aromatic thiazenes

Abstract

This thesis describes the work carried out by the author between September 1970 and September 1973. The electrolysis products of sulfur and S(_4)N(_4) in liquid ammonia, and (_4)N(_4) in organic solvents were studied with a view to devising improved routes to S(_7)NH, S(_4)(NH)(_4) and other imides. The reactions of these two compounds as model sulfur imides were also investigated. Addition reactions of (NSCl)(_3) were studied because it is the cheapest source of SN and NSCl fragments, and because it was hoped to convert the imides into SN compounds with exocyclic S-Cl bonds. It was found that (NSCl)(_3)/metal chloride adducts behaved as a source of NS(^+) ions in thionyl chloride solution, which reacted with SCl(_2) and S(_4)N(_4) to form the cations S(_2)NCl(_2)(^+) and S(_5)N(_5)(^+) respectively. The structures of these two cations were discussed, in particular the structure and reactions of S(_5)N(_5)(^+) as a member of the "electron rich" aromatic series of sulfur-nitrogen compounds. Other as yet unknown species were predicted as also being members of this series, and their possible stability and preparative routes discussed. A study was also carried out on the little investigated compound "S(_3)N(_2)Cl". The chlorodisulfate derivative:- S(_6)N(_4)(^2+) (ClS(_2)0(_6-))(_2) - was prepared, and the structure (obtained from x-ray crystallographic studied) discussed with reference to the unusual bonding observed in this compound. Finally, a summary of the work carried out at Staveley Chemicals Limited is included.