Chemistry in environmentally benign media .3. Synthesis and characterization of rhenium(V) complexes derived from novel water-soluble (hydroxymethyl)phosphines. Crystal structures of [Re(O)(2){(HOH2C)(2)PC6H4P(CH2OH)(2)}(2)]I and [Re(O)(2){(HOH2C)(2)PCH2CH2P(CH2OH)(2)}(2)]Cl

Water-soluble monophosphine P(CH2OH)(3) (1) and bisphosphines (HOH2C)(2)PC6H4P(CH2OH)(2) (2) and (HOH2C)(2)PCH2CH2P(CH2OH)(2) (3) were synthesized in near quantitative yields by the catalytic formylation of appropriate P-H bonded compounds in the presence of formaldehyde in aqueous media. The reactions of these mono- and bisphosphines 1-3 with ReO2I(PPh(3))(2), in biphasic media (aqueous/organic), or [ReO2(NC6H5)(4)]Cl, in aqueous media, produced the water-soluble Re(V) complexes [ReO2{P(CH2OH)(3)}4](+) (4), [ReO2{(HOH2C)(2)PC6H4P(CH2OH)(2)}(2)](+) (5), and [ReO2{(HOH2C)(2)PCH2P(CH2OH)(2)}(2)](+) (6) in near quantitative yields. The X-ray structures of 5 and 6, reported in this paper, confirmed the dioxorhenium(V) structures of these new generation of water-soluble transition metal complexes. All the compounds were characterized by IR, H-1, and P-31 NMR spectroscopy. X-ray data for 5: monoclinic, C2/c, a = 23.906(5) Angstrom, b = 7.049(1) Angstrom, c = 17.024(4) Angstrom, beta = 105.93(1)degrees, Z = 4, R = 0.019 (R(W) = 0.027). For 6: triclinic, <P(1)over bar>, a = 6.493(1) Angstrom, b = 9.488(2) Angstrom, c = 10.577(2) Angstrom, alpha = 104.4(1)degrees, beta = 96.4(1)degrees, gamma = 109.5(1)degrees, Z = 1, R = 0.045 (R(W) = 0.060).