Synthesis and Characterization of Palladium(II) and Platinum(II) Complexes Containing Water-Soluble Hybrid Phosphine-Phosphonate Ligands.
Water-soluble phosphonate-functionalized triaryl phosphine ligands Na(2)[Ph(2)P(4-C(6)H(4)PO(3))].1.5H(2)O (4a), Na(2)[Ph(2)P(3-C(6)H(4)PO(3))].2H(2)O (4b), and Na(2)[Ph(2)P(2-C(6)H(4)PO(3))].2H(2)O (4c), were prepared in 54-56% yields by the transesterification and hydrolysis of the appropriate phosphonic acid diethyl ester precursors. The solubilities of 4a-c in water are compared and the spectroscopic properties studied in detail. The crystal structure of Na(2)[Ph(2)P(4-C(6)H(4)PO(3))(H(2)O)(3)(CH(3)OH)].CH(3)OH (monoclinic, P2(1)/n, a = 6.4457(8) Å, b = 8.1226(8) Å, c = 46.351(3) Å, beta = 92.902(8) degrees, Z = 4) shows a dimeric association via two bridging water molecules and four sodium ions. Reaction of 4a with PtCl(2)(PPh(3))(2) in a biphasic H(2)O/CH(2)Cl(2) mixture gives cis- and trans-Na(4)[PtCl(2){Ph(2)P(4-C(6)H(4)PO(3))}(2)]. 3H(2)O. Palladium dichloride and 4a in H(2)O/benzene catalyzes the carbonylation of benzyl chloride to give phenylacetic acid (91%).
Schull
Terence L.
TL
Department of Chemistry, The George Washington University, 725 21st Street, N.W. Washington, D.C. 20052, and Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742.
Fettinger
James C.
JC
Knight
D. Andrew
DA