Synthesis and characterization of palladium(II) and rhodium(I) complexes coordinated with bis(diphenylphosphinomethyl) sulfide

Article abstract of DOI:10.1016/0020-1693(95)04819-7

Bis(chloromethyl) sulfide reacts with 2 moles of lithium diphenylphosphide in THF to give a white crystal, bis(diphenylphosphinomethyl) sulfide (dpms). This compound reacts with Na₂[PdCl₄] in ethanol to afford a monomeric complex, [PdCl₂(dpms-P,P′)]. The compound, dpms, reacts with a half mole of [Rh₂(μ-Cl)₂(CO)₄] to give a macrocyclic dinuclear complex, [{RhCl(CO) (μ-dpms)}₂] (3). The dynamic property of 3 is investigated by means of temperature-dependent NMR spectroscopy. Treatment of 3 with a half mole of [Rh₂(μ-Cl)₂(CO)₄], followed by the addition of NaBPh₄, gives a trinuclear complex, [Rh₃(μ-Cl)Cl(CO)₂(μ-dpms)₂](BPh ₄)·H₂O. When 3 is treated with AgClO₄ and [Cu(CH₃CN)₄]ClO₄, hetero-trinuclear complexes, M{Rh₂Cl₂(CO)₂(μ-dpms)₂}ClO ₄ · (H₂O)n (M=Ag, n=0; M=Cu, n=1, respectively) are isolated as yellow powders.