Synthesis, purification, and characterization of phosphine oxides and their hydrogen peroxide adducts. Academic Article uri icon


  • Reactions of the tertiary phosphines R(3)P (R = Me, Bu, Oct, Cy, Ph) with 35% aqueous H(2)O(2) gives the corresponding oxides as the H(2)O(2) adducts R(3)P=O(H(2)O(2))(x) (x = 0.5-1.0). Air oxidation leads to a mixture of products due to the insertion of oxygen into one or more P-C bonds. (31)P NMR spectroscopy in solution and in the solid state, as well as IR spectroscopy reveal distinct features of the phosphine oxides as compared to their H(2)O(2) adducts. The single crystal X-ray analyses of Bu(3)P=O and [Cy(3)P=O(H(2)O(2))](2) show a P=O stacking motif for the phosphine oxide and a cyclic structure, in which the six oxygen atoms exhibit a chair conformation for the dimeric H(2)O(2) adduct. Different methods for the decomposition of the bound H(2)O(2) and the removal of the ensuing strongly adsorbed H(2)O are evaluated. Treating R(3)P=O(H(2)O(2))(x) with molecular sieves destroys the bound H(2)O(2) safely under mild conditions (room temperature, toluene) within one hour and quantitatively removes the adsorbed H(2)O from the hygroscopic phosphine oxides within four hours. At 60 C the entire decomposition/drying process is complete within one hour.

published proceedings

  • Dalton Trans

altmetric score

  • 0.25

author list (cited authors)

  • Hilliard, C. R., Bhuvanesh, N., Gladysz, J. A., & Blmel, J.

citation count

  • 88

complete list of authors

  • Hilliard, Casie R||Bhuvanesh, Nattamai||Gladysz, John A||Bl├╝mel, Janet

publication date

  • February 2012