Inorganic Chemistry, Vol.36, No.9, 1786-1791, 1997
Synthesis and Coordination Chemistry of the First Water-Soluble Dithio-bis(Phosphine) Ligands ((Hoh2C)(2)P(CH2)(2)S-X-S(CH2)(2)P(Ch2Oh)(2)) (X=(CH2)(3) or C6H4) - X-Ray Crystal-Structure of (Pd(Hoh2C)(2)P(CH2)(2)S(CH2)(3)S(CH2)(2)P(Ch2Oh)(2))(Cl)(2)
The thioether-functionalized, water-soluble, bis(phosphines) (HOH2C)(2)PCH2CH2S(CH2)(3)SCH2CH2P(CH2OH)(2) (9) and C6H4{1,2-SCH2CH2P(CH2OH)(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)Cl-2 and Pd(C6H5CN)(2)Cl-2 in biphasic media (aqueous/organic) produced the water-soluble Pt(II) and Pd(II) complexes [Pt(HOH2C)(2)P(CH2)(2)S(CH2)(3)S(CH2)(2)P(CH2OH)(2)](Cl)(2) (11), [Pd(HOH2C)(2)P(CH2)(2)S(CH2)(3)S(CH2)(2)P(CH2OH)(2)](Cl)(2) (12), [Pt{(C6H4){1,2-S(CH2)(2)P(CH2OH)(2)}(2)}](Cl)(2) (13), and [Pd{(C6H4){1,2-S(CH2)(2)P(CH2OH)(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, H-1, C-13, and P-31 NMR spectroscopy, X-ray data for 12 : triclinic, , a = 9.9761(6) Angstrom, b = 10.2049(7) Angstrom, c = 11.6954(7) Angstrom, alpha = 67.730(10)degrees, beta = 69.943(10)degrees, gamma = 79.828(10)degrees, Z = 2, R = 0.0307 (R-w = 0.0797).