ic9510167_si_001.cif (30.58 kB)

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)2PC6H4P(CH2OH)2}2]I and [Re(O)2{(HOH2C)2PCH2CH2P(CH2OH)2}2]Cl

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posted on 27.03.1996, 00:00 by V. Sreenivasa Reddy, Douglas E. Berning, Kattesh V. Katti, Charles L. Barnes, Wynn A. Volkert, A. R. Ketring
Water-soluble monophosphine P(CH2OH)3 (1) and bisphosphines (HOH2C)2PC6H4P(CH2OH)2 (2) and (HOH2C)2PCH2CH2P(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(PPh3)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)2PC6H4P(CH2OH)2}2]+ (5), and [ReO2{(HOH2C)2PCH2CH2P(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, 1H, and 31P NMR spectroscopy. X-ray data for 5:  monoclinic, C2/c, a = 23.906(5) Å, b = 7.049(1) Å, c = 17.024(4) Å, β = 105.93(1)°, Z = 4, R = 0.019 (Rw = 0.027). For 6:  triclinic, P1̄, a = 6.493(1) Å, b = 9.488(2) Å, c = 10.577(2) Å, α = 104.4(1)°, β = 96.4(1)°, γ = 109.5(1)°, Z = 1, R = 0.045 (Rw = 0.060).

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