SYNTHESIS AND CHARACTERIZATION OF PALLADIUM(II) AND RHODIUM(I) COMPLEXES COORDINATED WITH BIS(DIPHENYLPHOSPHINOMETHYL) SULFIDE

Bis(chloromethyl) sulfide reacts with 2 moles of lithium diphenylphosp hide in THF to give a white crystal, bis(diphenylphosphinomethyl) sulf ide (dpms). This compound reacts with Na-2[PdCl4] in ethanol to afford a monomeric complex, [PdCl2(dpms-P,P')]. The compound, dpms, reacts w ith a half mole of [Rh-2(mu-Cl)(2)(CO)(4)] to give a macrocyclic dinuc lear complex, [{RhCl(CO)(mu-dpms)}(2)] (3). The dynamic property of 3 is investigated by means of temperature-dependent NMR spectroscopy. Tr eatment of 3 with a half mole of [Rh-2(mu-Cl)(2)(CO)(4)], followed by the addition of NaBPh(4), gives a trinuclear complex, [Rh-3(mu-Cl)Cl(C O)(2)(mu-dpms)(2)](BPh(4)). H2O. When 3 is treated with AgClO4 and [Cu (CH3CN)(4)]ClO4, hetero-trinuclear complexes, M{Rh2Cl2(CO)(2)(mu-dpms) (2)}ClO4 .(H2O)n (M = Ag, n = 0; M = Cu, n = 1, respectively) are isol ated as yellow powders.