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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){sub 2}[(HOH{sub 2}C){sub 2}PC{sub 6}H{sub 4}P(CH{sub 2}OH){sub 2}]{sub 2}]I and [Re(O){sub 2}[(HOH{sub 2}C){sub 2}PCH{sub 2}CH{sub 2}P(CH{sub 2}OH){sub 2}]{sub 2}]Cl

Journal Article · · Inorganic Chemistry
DOI:https://doi.org/10.1021/ic9510167· OSTI ID:263743
; ;  [1]
  1. Univ. of Missouri, Columbia, MO (United States); and others
Water-soluble monophosphine P(CH{sub 2}OH){sub 3} (1) and bisphosphines (HOH{sub 2}C){sub 2}PC{sub 6}H{sub 4}P(CH{sub 2}OH){sub 2}(2) and (HOH{sub 2}C){sub 2}{sup {minus}}PCH{sub 2}CH{sub 2}P(CH{sub 2}OH){sub 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 ReO{sub 2}I(PPh{sub 3}){sub 2}, in biphasic media (aqueous/organic), or [ReO{sub 2}(NC{sub 6}H{sub 5}){sub 4}]Cl, in aqueous media, produced the water-soluble Re(V) complexes [ReO{sub 2}(P(CH{sub 2}OH){sub 3}){sub 4}]{sup +} (4), [ReO{sub 2}(HOH{sub 2}C){sub 2}PC{sub 6}H{sub 4}P(CH{sub 2{minus}}OH){sub 2}{sub 2}]{sup +}(5), and [ReO{sub 2}[(HOH{sub 2}C){sub 2}PCH{sub 2}CH{sub 2}P(CH{sub 2}OH){sub 2}]{sub 2}]{sup +} (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,{sup 1}H, and {sup 31}PNMR spectroscopy. X-ray data for 5: monoclinic, C2/c, {alpha}=23.906(5) {Angstrom}, b=7049(1) {Angstrom}, c= 17.024(4) {Angstrom}, {Beta} = 105.93(1){degrees}, Z=4, R=0.019 (R{sub w} = 0.027). For 6: triclinic, P1, {alpha} =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{sub 2} = 0.060).
OSTI ID:
263743
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 7 Vol. 35; ISSN 0020-1669; ISSN INOCAJ
Country of Publication:
United States
Language:
English