Reactivity of [Pd3(μ-O2CMe)3(μ-MeSCHC(O)OR)3] (R=Me, Et) towards bidentate nucleophiles: X-ray structure of [Pd2(acac)2(μ-MeSCHC(O)OEt)2]

[Pd3(μ-O2CMe)3(μ-MeSCHC(O)OEt-C,S)3] (1) and [Pd3(μ-O2CMe)3(μ-MeSCHC(O)OMe-C,S)3] (2) react with acetylacetone (Hacac) and benzolylacetone (Hbzac) to give the polynuclear complexes [Pd2(acac)2(MeSCHC(O)OR)2] and [Pd3(bzac)3(MeSCHC(O)OR)3] (R=Et, Me), stemming from the exchange of the acetato ligands. The acetylacetonato derivative [Pd2(acac)2(μ-MeSCHC(O)OEt-C,S)2] (3) is a centrosymmetric dimer with chelate acac− ligands and bridging C,S sulfur ligands, which crystallizes in the space group P1, with Z=1 in an elementary cell whose dimensions are a=10.322(2), b=11.460(2), c=6.249(1) Å and α=99.1(1), β=96.9(1), γ=115.7(1)°. The structure has been resolved on the basis of 2115 reflections with final R=0.022 (Rw=0.024). When 1 and 2 react with bipyridine, a comproportionation of the ligands takes place and in both cases the main reaction product is [Pd(O2CMe)2(dipy)].