Synthesis and Coordination Chemistry of the First Water-Soluble Dithio-Bis(phosphine) Ligands [(HOH(2)C)(2)P(CH(2))(2)S-X-S(CH(2))(2)P(CH(2)OH)(2)] (X = (CH(2))(3) or C(6)H(4)). X-ray Crystal Structure of [Pd(HOH(2)C)(2)P(CH(2))(2)S(CH(2))(3)S(CH(2))(2)P(CH(2)OH)(2)](Cl)(2)(1).
The thioether-functionalized, water-soluble, bis(phosphines) (HOH(2)C)(2)PCH(2)CH(2)S(CH(2))(3)SCH(2)CH(2)P(CH(2)OH)(2) (9) and C(6)H(4){1,2-SCH(2)CH(2)P(CH(2)OH)(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(C(6)H(5)CN)(2)Cl(2) in biphasic media (aqueous/organic) produced the water-soluble Pt(II) and Pd(II) complexes [Pt(HOH(2)C)(2)P(CH(2))(2)S(CH(2))(3)S(CH(2))(2)P(CH(2)OH)(2)](Cl)(2) (11), [Pd(HOH(2)C)(2)P(CH(2))(2)S(CH(2))(3)S(CH(2))(2)P(CH(2)OH)(2)](Cl)(2) (12), [Pt{(C(6)H(4)){1,2-S(CH(2))(2)P(CH(2)OH)(2)}(2)}](Cl)(2) (13), and [Pd{(C(6)H(4)){1,2-S(CH(2))(2)P(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, (1)H, (13)C, and (31)P NMR spectroscopy. X-ray data for 12: triclinic, P&onemacr;, a = 9.9761(6) Å, b = 10.2049(7) Å, c = 11.6954(7) Å, alpha = 67.730(10) degrees, beta = 69.943(10) degrees, gamma = 79.828(10) degrees, Z = 2, R = 0.0307 (R(w) = 0.0797).
Smith
C. Jeffrey
CJ
Center for Radiological Research and Missouri University Research Reactor, Department of Chemistry, University of Missouri, Columbia, Missouri 65203.
Reddy
V. Sreenivasa
VS
Karra
Srinivasa R.
SR
Katti
Kattesh V.
KV
Barbour
Leonard J.
LJ