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]

[Pd-3(mu-O2CMe)(3)(mu-MesCHC(O)OEt-C,S)(3)] (1) and [Pd-3(mu-O-2-CMe)(3)(mu-MeSCHC(O)OMe-C,S)(3)] (2) react with acetylacetone (Hacac) and benzolylacetone (Hbzac) to give the polynuclear complexes [Pd-2(acac)(2)(MeSCHC(O)OR)(2)] and [Pd-3(bzac)(3)(MesCHC(O)OR)(3)] (R =Et, Me), stemming from the exchange of the acetato ligands. The acetylacetonato derivative [Pd-2(acac)(2)(mu-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 P (1) over bar, with Z=1 in an elementary cell whose dimensions are a=10.322(2), b=11.460(2), c = 6.249(1) Angstrom and alpha = 99.1(1), beta = 96.9(1), gamma = 115.7(1)degrees. The structure has been resolved on the basis of 2115 reflections with final R = 0.022 (R-w = 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)]. (C) 1999 Elsevier Science S.A. All rights reserved.