Inorganic Chemistry, Vol.36, No.18, 3928-3935, 1997
Syntheses and characterization of chemically flexible, water-soluble dithio-bis(phosphine) compounds: (HOH2C)(2)P(CH2)(2)S(CH2)(3)S(CH2)(2)P(CH2OH)(2), (HOH2C)(2)PCH2CH2S(CH2)(4)SCH2CH2P(CH2OH)(2), and (HOH2C)(2)PCH2CH2CH2S(CH2)(3)-SCH2CH2CH2P(CH2OH)(2). Systematic investigation of the effect of chain length on the coordination chemistry of rhenium(V). X-ray crystal structures of [ReO2(HOH2C)(2)P(CH2)(2)S(CH2)(3)S(CH2)(2)P(CH2OH)(2)](2)(Cl)(2 ), [ReO2(HOH2C)(2)P(CH2)(2)S(CH2)(4)S(CH2)(2)P(CH2OH)(2)](2)(ReO4-)(2), and [ReO2(HOH2C)(2)P(CH2)(3)S(CH2)(3)S(CH2)(3)P(CH2OH)(2)](Cl)
The water-soluble dithio-bis(phosphine)s (HOH2C)(2)P(CH2)(2)S(CH2)(2)P(CH2OH)(2) (1), (HOH2C)(2)PCH2-CH2S(CH2)(4)SCH2CH2P(CH2OH)(2) (4), and (HOH2C)(2)PCH2CH2CH2S(CH2)(3)SCH2CH2CH2P(CH2OH)(2) (7) were synthesized in near-quantitative yield by the formylation of their appropriate phosphine hydride precursors in the presence of formaldehyde and oxygen-free ethanol. The reactions of 1, 4, and 7 with [ReO2(C5H5N)(4)](Cl) in refluxing water produced the water-soluble Re(V) complexes [ReO2(HOH2C)(2)P(CH2)(2)S(CH2)(3)S(CH2)(2)P(CH2OH)(2)](2)(Cl)(2 ) (8), [ReO2(HOH2C)(2)P(CH2)(2)S(CH2)(4)S(CH2)(2)P(CH2OH)(2)](2)(ReO4-)(2) (9), and [ReO2(HOH2C)(2)P-(Cl-2)(3)S (CH2)(3)S(CH2)(3)P(CH2OH)(2)](Cl) (10) The X-ray crystallographic analysis of 8-10, reported in this paper, confirmed the dioxorhenium(V) structures. All of the compounds were characterized by H-1, C-13, and P-31 NMR spectroscopy. HPLC chromatographic analysis of 8-10 demonstrated purities of >98% for each of the new complexes formed. X-ray data for [ReO2(HOH2C)(2)P(CH2)(2)S(CH2)(3)S(CH2)(2)P(CH2OH)(2)](2)(Cl)(2 ) (8): monoclinic, P2(1)/n, a = 10.7982(5) Angstrom, b = 23.486(1) Angstrom, c = 15.4408(8) Angstrom, beta = 94.539(1)degrees, Z = 4, R = 0.0246 (wR2 = 0.0574). For [ReO2(HOH2C)(2)P(CH2)(2)S(CH2)(4)S(CH2)(2)P(CH2OH)(2)](2)(ReO4-)(2) (9): triclinic, <(P)over bar 1>, a = 10.3762(5) Angstrom, b = 12.1099(6) Angstrom, c = 18.7555(9) Angstrom, alpha = 90.259(1)degrees, beta = 91.900(1)degrees, gamma = 104,965(1)degrees, Z = 2, R = 0.0546 (wR2 = 0.1412). For [ReO2(HOH2C)(2)P(CH2)(3)S(CH2)(3)S(CH2)(3)P(CH2OH)(2)] (10): monoclinic, P2(1)/n, a = 10.6224(6) Angstrom, b = 12.5532(8) Angstrom, c = 18.5757(11) Angstrom, beta = 103.663(10)degrees, Z = 4, R = 0.0261 (wR2 = 0.0656).