The mononuclear Cu(I) complexes [LCuI((SSiPr3)-Pr-i)] (L = 1,1,1-tris ( diphenylphosphinomethyl) ethane (triphos), 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes)) have been prepared by ligand displacement from [(LCuCl)-Cl-I] with (Pr3SiS center dot-)-Pr-i. Both compounds are colorless, diamagnetic species and have been characterized structurally by X-ray crystallography. The compounds [(IMes)Cu(eta(1 kappa S)3-SC-(O)CH3)] and [(triphos)Cu(eta(1)K(S)3-SC(S)OCH3)] have been prepared in the context of synthesis aimed at [LCu(eta(1)kappa(S)-SCOS)] and [LCu(eta(1)kappa(S)-SCS2)] complexes, which are intended as synthons toward an analogue of the Mo(mu-OSCO)Cu intermediate proposed as occurring in the catalytic cycle of carbon monoxide dehydrogenase (CODH).