Building of dithiocarbamate and dithiocarbimate ligands within a heterobimetallic core

摘要

Heterobinuclear anions [MnRe(CO)_6(μ-S)(μ-SCPR_3)]~(2-) (2) undergo protonation and electrophilic addition of dimethylthiocarbamoyl or isothiocyanate to afford, respectively, neutral [MnRe(CO)_6(μ-S_2CNMe_2)(μ-S_2CPR_3)] (3) containing μ_2-(S,S') dithiocarbamate, or anionic [MnRe(CO)_6(μ-SC(S)NR'){μ-SC(H)PR_3}]~- {4} containing μ_2-(N,S)-dithiocarbimate. The terminal sulfur in the latter can be methylated with MeI or metallated with [CuCl(p-tolyl)_3] to give neutral dithiocarbimato complexes 5 or 6. The structures of 3a (R = Pr~i), 5a (R = Pr~i, R' = Et), and 5c (R = Pr~i, R' = Ph), have been determined by X-ray crystallography.