ON CHALCOGENOLATES .198. STUDIES ON POLYTHIOCUPRATES(I) [CU(SX)] .2. HYDRAZINIUM AND ETHYLENEDIAMMONIUM POLYTHIOCUPRATES(I)

The red polythiocuprates(I) 1-5 (formulae see "Inhaltsubersicht") have been prepared by reaction of hydrazinium or ethylenediammonium polysulfides with copper(II) salts, dissolved in water, under variable conditions. Their properties are described. In aqueous alkaline media 1-5 decompose into CuS and S; in the presence of carbon disulfide CuS, S(x)2-, and CS3(2-) besides CS4(2-) and S2CO2- are formed. The existence of the discreet ion [Cu2CS7]2-, described in literature, was not confirmed. The polythiocuprates(I) 1-5, dissolved in dimethylformamide, decompose via the radical anion S3-. The decomposition of S3- has been studied kinetically by means of compound 5. The half-life of decay of S3- is tau1/2 = 71.5 h at 20-degrees-C. The pentathiocuprate(I) 3 reacts with n-butyl chloride to produce the substituted sulfanes C4H9)2S(x), where x = 1, 2, and 3.