Building of dithiocarbamate and dithiocarbimate ligands within a heterobimetallic core

Heterobinuclear anions [MnRe(CO)6((mu)-S)((mu)-SCPR3)]2-(2) undergo selective protonation and electrophilic addition of dimethylthiocarbamoyl or isothiocyanate to afford, respectively, neutral [MnRe(CO)6((mu)-S2CNMe2)((mu)-S2CPR3)](3) containing (mu) 2-(S,S) dithiocarbamate, or anionic [MnRe(CO)6((mu)-SC(S)NR){(mu)-SC(H)PR3}]-(4) containing (mu)2-(N,S)-dithiocarbimate. The terminal sulfur in the latter can be methylated with MeI or metallated with [AuCl(p-tolyl)3] to give neutral dithiocarbimato complexes 5 or 6. The structures of 3a(R = Pri), 5a(R = Pri, Rʹ= Et), and 5c(R = Pri, R= Ph), have been determined by X-ray crystallography.