Abstract

AbstractThe reaction of Bunsen's cacodyl disulfide, Me2As(S)‐S‐AsMe2, with heavy metal cations in methanol produces insoluble salts (complexes) of dimethyldithioarsinic acid, Me2AsS2H, and dimethyl arsenium ion, Me2As:+. This arsenium ion prefers to react with Me2As(S)‐S‐AsMe2, when in excess, compared to AcO− or MeOH/H2O and it is also reactive towards sulfur (Sx, x = 1‐8) producing the stabilized dimethylarsino sulfenium cation, $\rm Me_{2}As- {\mathop{\rm{S}}\limits^{.}_{\ddot{}}} ^{+} \longleftrightarrow Me_{2}\mathop{\rm{A}}\limits^{+}_{} s=\mathop{\rm{S}}\limits^{.}_{\ddot{}}$. The complexes (Me2AsS2)xM (x = 1 or 2) are unstable in the presence of their own heavy metal cations decomposing to colored solids. In an attempt to prepare salts of Me2AsSH, the reactions of (Me2AsS2)xM with triphenylphosphine and trimethyl phosphite gave the metal sulfide and Me2As‐S‐AsMe2 instead.

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