Synthesis and characterization of new allyl palladium complexes with thionate ligands; X-ray molecular structures of [Pd 3(η 3-C 4H 7) 3{pm(Me) 2S} 2](CF 3SO 3) and [Pd{pm(Me) 2S} 2], η 3-C 4H 7=η 3-2-MeC 3H 4, pm(Me) 2S=Pyridine-4,6-dimethyl-2-thionate

Abstract

The reaction of [Pd(η 3-C 4H 7)]CF 3SO 3 (η 3-C 4H 7=η 3-2-MeC 3H 4) ( 1), prepared in situ by reaction of [Pd(η 3-C 4H 7)Cl] 2 with AgCF 3SO 3, with various thionate ligands, gives new polymeric complexes formulated as [Pd(η 3-C 4H 7)(RS)] n ( 2) [RS=pyS (pyridine-2-thionate)], im(Me)S(imidazole-3-methyl-2-thionate) ( 3), pm(Me) 2S (pyrimidine-4,6-dimethyl-2-thionate) ( 4). A solution of 4 contaminated with KCF 3SO 3 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(η 3-C 4H 7) 3{pm(Me) 2S} 2] + ( 5). Finally, the formation of a mononuclear thionate-containing palladium complex [Pd{pm(Me) 2S} 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.