Mono- and polynuclear chloro complexes of palladium(II) with alpha-substituted thioethers

Palladium dichloro bis-benzonitrile reacts with alpha-substituted thioether s to give the square-planar complexes [PdCl2(RSCH(2)Z)(2)] (1-6) (1-4: R = Me, Z = C(O)OMe (1), C(O)OEt (2), C(O)Omenthyl(-) (3), C(O)Me (4); (5): R = Et, Z = C(O)Me; (6). R - Me, Z = CH(OMe)(2)). Complex 1 crystallizes in th e space group P2(1)/a, with Z = 2 in an elementary cell whose dimensions ar e a = 9.116(1), b = 8.659(1), c = 10.351(2) Angstrom and beta = 112.2(1)deg rees. Its structure (SHELXL-93, R-1 0.021 and R-2w 0.0597) shows a marked d eviation from the ideal square geometry to reduce the steric repulsion betw een the ester group of the sulfur ligand and the chlorine atom in cis posit ion. The one-pot reaction of the chloro complexes 2 or 3 with silver acetat e affords the corresponding trimers [Pd-3(mu-OAc)(3)(mu-RSCHZ)(3)] (7, 8), previously obtained by reacting palladium acetate with MeSCH(2)Z. Complex 7 undergoes, with KCI or HCl, an OAc- -Cl- exchange reaction to give the two chloro-bridged isomers [PdCl(MeSCHC(O)OEt)](n) (9, 10: n = 2, 4). The Cl-b ridge in dimer 9 is broken by triphenylphosphine to give the monomeric comp lex [Pd-Cl(MeSCHC(O)OEt)(PPh3)]. (C) 2000 Elsevier Science S.A. All rights reserved.