Diaryl dithiocarbamates: synthesis, oxidation to thiuram disulfides, Co(iii) complexes [Co(S2CNAr2)3] and their use as single source precursors to CoS2

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 ⁿBuLi. 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.