The synthesis of a new N-heterocyclic carbene with bulky S-arylthiocarbamate substituents was devised from the condensation between 2-chloromethyl-4-methy-l,6-[3,5-bis(trifluoromethyl)phenyl]-S-phenyl-N,N-dimethylthiocarbamate and imidazole, resulting in the proligand -carb) 2 NHC]I.This newly synthesized proligand was crystallographically characterized, thus confirming its identity; its stability was established in several solvents, resulting in air oxidation in methanolic solution, giving rise to the decomposition product N,N'-bis[(2-S-(N'',N''-dimethyl thiocarbamoyl)-5-methyl)phenylmethyl]-4,5-dimethoxyimidazolyl-2-one.Reaction of the proligand with silver oxide afforded the corresponding complex [(S-carb) 2 NHC]AgI, which was fully characterized by spectroscopic techniques.