One-Step Synthesis of Dithiocarbamates from Metal Powders

Neutral metal dithiocarbamate complexes (M(NR2CS2)x) are well-known precursors to metal sulfides, a class of materials with numerous technological applications. We are involved in a research effort to prepare new precursors to metal sulfides using simple, reproducible synthetic procedures. We describe the results of our synthetic and characterization studies for M = Fe, Co, Ni, Cu, and In. For example, treatment of metallic indium with tetramethylthiuramdisulfide (tmtd) in 4-methylpyridine (4-Mepy) at 25 °C produces a new homoleptic indium (III) dithiocarbamate, In(N(CH3)2CS2)3 (I), in yields of over 60%. The indium (III) dithiocarbamate was characterized by X-ray crystallography; (I) exists in the solid state as discrete distorted-octahedral molecules. Compound (I) crystallizes in the P1bar (No. 2) space group with lattice parameters: a = 9.282(1) Å, b = 10.081(1) Å, c = 12.502 Å, α = 73.91(1)°, β = 70.21(1)°, γ = 85.84(1)°, and Z = 2. X-ray diffraction and mass spectral data were used to characterize the products of the analogous reactions with Fe, Co, Ni, and Cu. We discuss both use of dithiocarbamates as precursors and our approach to their preparation.