Synthesis and characterization of new allyl palladium complexes with thionate ligands;: X-ray molecular structures of [Pd3(η3-C4H7)3{pm(Me)2S}2](CF3SO3) and [Pd{pm(Me)2S}2], η3-C4H7 = η3-2-Me-C3H4, pm(Me)2S = pyridine-4,6-dimethyl-2-thionate

The reaction of [Pd(eta(3)-C4H7)]CF3SO3 (eta(3)-C4H7 = eta(3)-2-MeC3H4) (1), prepared in situ by reaction of [Pd(eta(3)-C4H7)Cl](2) with AgCF3SO3, with various thionate ligands, gives new polymeric complexes formulated as [Pd(eta(3)-C4H7)(RS)](n) (2) [RS =pyS (pyridine-2-thionate)], im(Me)S(imidazole-3-methyl-2-thionate) (3), pm(Me),S (pyrimidine-3,6-dimethyl-2-thionate) (4). A solution of 4 contaminated with KCF3SO3 evolves to give crystals that correspond to a new polymeric species whose X-ray crystal molecular structure indicates the presence of cationic infinite chains built of trinuclear units, [Pd-3(eta(3)-C4H7)(3){pm(Me)(2)S}(2)](+) (5). Finally, the formation of a mononuclear thionate-containing palladium complex [Pd{pm(Me)(2)S}(2)] (6) occurs from a solution of 5 after prolonged periods. An X-ray crystal structure determination indicates a square-planar disposition of two thionate ligands around the Pd atom. The different complexes were characterized by spectroscopic techniques. (C) 1999 Elsevier Science S.A. All rights reserved.