The synthesis of new bimetallic complex salts by halide/sulfur chelate cross transfer: X-ray crystal structures of the salts [Ni(S2CNEt2)(dppe)](2)[HgBr4], [Pt(S2CNEt2)(dppe)](2)[CdCl4], [Co(S2CNEt2)(2)(dppe)](2)[Cl3ZnO :(Ph)(2)PCH2CH2P(Ph)(2): OZnCl3] and [Pd((S2CNBu2)-Bu-n)(bipy)](2)[CdCl4]

The nickel and platinum complexes [MX2(dppe)) (X = Cl, Br) react with bi- a nd tri-valent metal diethyldithiocarbamates [M'(S2CNEt2)(n)] (M' = Pb, Zn, Cd, Hg, Ni, MoO2, VO, n = 2; M' = Co, Fe, Mn, n = 3) to afford salts [M(S2C NEt2)(dPPe)](2)[M'X-4]; reactions involving [Cu(S2CNEt2)(2)] and [Ag(S2CNEt 2)] gave salts of the form [M(S2CNEt2)(dppe)][M'X-2] (M' = Cu, Ag). The com plexes cis [RuCl2(dppm)(2)], [CoCl2(dppe)] and [PdX2(bipy)] likewise react with the same dithiocarbamates to form salts [Ru(S2CNEt2)(dppe)(2)](2)[M'Cl -4] [Co(S2CNEt2)(2)(dppe)](2)[M'Cl-4] and [Pd((S2CNBu2)-Bu-n)(bipy)](2)[M'X -4], respectively. Sample reactions involving other S-chelate ligands-S2COE t-, S2PPh2- and S2P(OEt)(2)(-) -appear to follow the same general pattern. However, the O-ethyldithio carbonates (ethylxanthates) are partly converted to the corresponding dithiocarbonates. An anomalous reaction between [CoCl 2(dppe)] and [Zn(S2CNEt2) in the presence of (S2CNEt2)(2) affords the novel complex [Co(S2CNEt2)(2)(dppe)](2)[Cl3ZnO:(Ph)(2)PCH2CH2P(Ph)(2):OZnCl3]. A selection of these salts have been fully characterised by elemental analys is and spectroscopic techniques, the remainder have been identified by spec troscopic methods alone. X-ray crystal structures are reported for the salt s [Ni(S2CNEt2)(dppe)](2) [HgBr4], [Pt(S2CNEt2)(dppe)](2)[CdCl4], [Co(S2CNEt 2)(2)(dppe)](2)-[Cl3ZnO:(Ph)(2)PCH2CH2P(Ph)(2):OZnCl3] and [Pd((S2CNBu2)-Bu -n) (bipy)](2)[CdCl4]. (C) 2001 Elsevier Science Ltd. All rights reserved.