Insertion of CS2 into Bi–N Bonds: Coordination Chemistry and Reactivity of Bismuth Dithiocarbamates

Abstract The straightforward access to simple halo(bismuth)amides bearing the core structural motif [Bi(NMe2)nX3–n] (X = Cl, Br, I; n = 1, 2) has been investigated, along with their coordination chemistry and their reactivity toward CS2. The latter revealed selective insertion reactions to give literature-known and new bismuth compounds with the dithiocarbamate (S2CNMe2)− ligand scaffold. Their behavior toward a cyclic(alkyl)(amino) carbene (CAAC) has been studied, demonstrating that redox processes are less relevant than in simple bismuth halides and halo(bismuth)amides and that the coordination of the CAAC ligand dominates instead. Exposing bismuth dithiocarbamates to reducing conditions revealed the complex anion [Bi(S2CNMe2)4]−, an unprecedented structural motif in pnictogen chemistry. The rational synthesis of [Li(py)4][Bi(S2CNMe2)4] provided synthetic access to this motif. Finally, the potential of the neutral species [Bi(S2CNMe2)3] as a single-source precursor for the temperature-induced formation of Bi2S3 has been investigated.