Building of dithiocarbamate and dithiocarbimate ligands within a heterobimetallic core

Abstract

Heterobinuclear anions [MnRe(CO)₆(μ-S)(μ-SCPR₃)]²⁻ (2) undergo selective protonation and electrophilic addition of dimethylthiocarbamoyl or isothiocyanate to afford, respectively, neutral [MnRe(CO)₆(μ-S₂CNMe₂)(μ-S₂CPR₃)] (3) containing μ₂-(S,S′) dithiocarbamate, or anionic [MnRe(CO)₆(µ-SC(S)NR′){µ-SC(H)PR₃}]⁻ (4) containing μ₂-(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, R′= Et), and 5c (R = Prⁱ, R′= Ph), have been determined by X-ray crystallography.