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Title: Electrosynthetic and other studies of sulfur imides and aromatic thiazenes
Author: Clarke, H. G.
ISNI:       0000 0001 3557 7588
Awarding Body: Durham University
Current Institution: Durham University
Date of Award: 1974
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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.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available