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Updated: Sep 1, 2025

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Diaryl dithiocarbamates: synthesis, oxidation to thiuram disulfides, Co(III) complexes [Co(S2CNAr2)3] and their use
Jagodish C Sarker1,2, Rosie Nash1, Suwimon Boonrungsiman3
1Department of Chemistry, King's College London, Britannia House, 7 Trinity Street, London SE1 1DB, UK. graeme.hogarth@kcl.ac.uk.
Abstract:
Air and moisture stable diaryl dithiocarbamate salts, Ar2NCS2Li, result from addition of CS2 to Ar2NLi, the latter being formed upon deprotonation of diarylamines by BuLi. Oxidation with K3[Fe(CN)6] affords the analogous thiuram disulfides, (Ar2NCS2)2, two examples of which (Ar = p-C6H4X; X = Me, OMe) have been crystallographically characterised. The interconversion of dithiocarbamate and thiuram disulfides has also been probed electrochemically and compared with that established for the widely-utilised diethyl system. While oxidation reactions are generally clean and high yielding, for Ph(2-naphthyl)NCS2Li an ortho-cyclisation product, 3-phenylnaphtho[2,1-d]thiazole-2(3H)-thione, is also formed, resulting from a competitive intramolecular free-radical cyclisation. To demonstrate the coordinating ability of diaryl dithiocarbamates, a small series of Co(III) complexes have been prepared, with two examples, [Co{S2CN(p-tolyl)2}3] and [Co{S2CNPh(m-tolyl)}3] being crystallographically characterised. Solvothermal decomposition of [Co{S2CN(p-tolyl)2}3] in oleylamine generates phase pure CoS2 nanospheres in an unexpected phase-selective manner.
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