The coordination ability of the organometallic sulfur ligand [Pd 3( μ-OAc) 3( μ-MeSCHCO 2Et- C, S) 3] and the XRD structure of its palladium(II) complex [Pd 4( μ-OAc) 3( μ-MeSCHCO 2Et- C, S)( μ3-MeSCHCO 2Et- C, κ2S) 2( η2-MeSCHCO 2Et- C, S)]BF 4

Abstract

The trimetric mixed sphere complex of palladium(II) [Pd 3( μ-OAc) 3( μ-MeSCHCO 2Et- C, S) 3]( 1) affords [Pd 4( μ-OAc) 3( μ-MeSCHCO 2Et- C, S)( μ 3-MeSCHCO 2Et- C, κ 2 S) 2( η 2-MeSCHCO 2Et- C, S)]BF 4 ( 2) by reaction with the equimolar amount of HBF 4 in CH 2Cl 2. The solvato complex 2-Me 2CO crystallizes as monoclinic, space group P2 1/ n, a=13.315(2), b=24.138(2), c=15.049(2) Å, β=105.4(1)°, U=4663(3) Å 3, Z=4. Its structure ( R w=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: κ 1 in a three membered chelate ring and μ 2 bridges and κ 2 in μ 3 bridges. The tetranuclear cation formally stems from the addition of the chelate cationic fragment [Pd(MeSCHCO 2Et- 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{[Pd 3( μ-OAc) 3( μ-MeSCHCO 2Et- C, S)( μ 3-MeSCHCO 2Et- C, κ 2 S) 2]} 2](BF 4) 2 ( 3) and of [Cu{[Pd 3( μ-OAc) 3( μ-MeSCHCO 2Et- C, S)( μ 3-MeSCHCO 2Et- C, κ 2 S) 2]} 2]PF 6 ( 4), by simple addition of 1 to the tetrakis acetonitrile complexes of palladium(II) and copper(I), respectively.