The coordination ability of the organometallic sulfur ligand [Pd-3(mu-OAc)(3)(mu-MeSCHCO2Et-C,S)(3)] and the XRD structure of its palladium(II) complex [Pd-4(mu-OAc)(3)(mu-MeSCHCO2Et-C,S)(mu(3)-MeSCHCO2Et-C,kappa S-2)(2)(eta(2)-MeSCHCO2Et-C,S)]BF4

The trimetric mixed sphere complex of palladium(II) [Pd3(μ-OAc)3(μ-MeSCHCO2Et-C,S)3](1) affords [Pd4(μ-OAc)3(μ-MeSCHCO2Et-C,S)(μ3-MeSCHCO2Et-C,κ2S)2(η2-MeSCHCO2Et-C,S)]BF4 (2) by reaction with the equimolar amount of HBF4 in CH2Cl2. The solvato complex 2-Me2CO crystallizes as monoclinic, space group P21/n, a=13.315(2), b=24.138(2), c=15.049(2) Å, β=105.4(1)°, U=4663(3) Å3, Z=4. Its structure (Rw=0.049) is characterized by the presence of four (ethoxycarbonyl)(methylthio)methanide ligands, with chiral methine carbon and sulfur atoms. The latter display three different coordination modes: κ1 in a three membered chelate ring and μ2 bridges and κ2 in μ3 bridges. The tetranuclear cation formally stems from the addition of the chelate cationic fragment [Pd(MeSCHCO2Et-C,S)]+ to a molecule of the starting compound. The formation of 2 highlights the coordination ability of 1 through its sulfur atoms, which is confirmed by the successful synthesis of [Pd{[Pd3(μ-OAc)3(μ-MeSCHCO2Et-C,S)(μ3-MeSCHCO2Et-C, κ2S)2]}2](BF4)2 (3) and of [Cu{[Pd3(μ-OAc)3(μ-MeSCHCO2Et-C,S)(μ3-MeSCHCO2Et-C, κ2S)2]}2]PF6 (4), by simple addition of 1 to the tetrakis acetonitrile complexes of palladium(II) and copper(I), respectively.