Synthesis and Coordination Chemistry of the First Water-Soluble Dithio-Bis(phosphine) Ligands [(HOH2C)2P(CH2)2S-X-S(CH 2)2P(CH2OH)2] (X = (CH2)3 or C6H4)

<p>The thioether-functionalized, water-soluble, bis(phosphines) (HOH2C)2PCH2CH2S(CH 2)3SCH2CH2P(CH2OH) 2 (9) and C6H4{1,2-SCH2CH2P(CH 2OH)2}2 (10) were synthesized in near quantitative yields by the formylation of the appropriate phosphine hydrides in the presence of formaldehyde in ethanol. The reactions of 9 and 10 with Pt(COD)Cl2 and Pd(C6H5CN)2Cl2 in biphasic media (aqueous/organic) produced the water-soluble Pt(II) and Pd(II) complexes [Pt(HOH2C)2P(CH2)2S(CH 2)3S(CH2)2P(CH2OH) 2](Cl)2 (11), [Pd(HOH2C)2P(CH2)2S(CH 2)3S(CH2)2-P(CH2OH) 2](Cl)2 (12), [Pt{(C6H4){1,2-S(CH2)2P(CH 2OH)2}2}](Cl)2 (13), and [Pd{(C6H4){1,2-S(CH2)2P(CH 2-OH)2}2}](Cl)2 (14) in near quantitative yields. The X-ray crystal structure of 12 confirms a square-planar Pd(II) structure for this new generation of water-soluble transition metal complexes. All of the complexes were characterized by MS, 1H, 13C, and 31P NMR spectroscopy. X-ray data for 12: triclinic, P1, a = 9.9761(6) Å, b = 10.2049(7) Å, c = 11.6954(7) Å, α = 67.730(10)°, β= 69.943(10)°, γ = 79.828(10)°, Z = 2, R = 0.0307 (Rw = 0.0797).</p>