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Issue 6, 2012
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Synthesis, purification, and characterization of phosphine oxides and their hydrogen peroxide adducts

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Abstract

Reactions of the tertiary phosphines R3P (R = Me, Bu, Oct, Cy, Ph) with 35% aqueous H2O2 gives the corresponding oxides as the H2O2 adducts R3P[double bond, length as m-dash]O·(H2O2)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. 31P 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 H2O2 adducts. The single crystal X-ray analyses of Bu3P[double bond, length as m-dash]O and [Cy3P[double bond, length as m-dash]O·(H2O2)]2 show a P[double bond, length as m-dash]O stacking motif for the phosphine oxide and a cyclic structure, in which the six oxygen atoms exhibit a chair conformation for the dimeric H2O2 adduct. Different methods for the decomposition of the bound H2O2 and the removal of the ensuing strongly adsorbed H2O are evaluated. Treating R3P[double bond, length as m-dash]O·(H2O2)x with molecular sieves destroys the bound H2O2 safely under mild conditions (room temperature, toluene) within one hour and quantitatively removes the adsorbed H2O from the hygroscopic phosphine oxides within four hours. At 60 °C the entire decomposition/drying process is complete within one hour.

Graphical abstract: Synthesis, purification, and characterization of phosphine oxides and their hydrogen peroxide adducts

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Publication details

The article was received on 03 Oct 2011, accepted on 21 Oct 2011 and first published on 09 Dec 2011


Article type: Paper
DOI: 10.1039/C1DT11863C
Dalton Trans., 2012,41, 1742-1754

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    Synthesis, purification, and characterization of phosphine oxides and their hydrogen peroxide adducts

    C. R. Hilliard, N. Bhuvanesh, J. A. Gladysz and J. Blümel, Dalton Trans., 2012, 41, 1742
    DOI: 10.1039/C1DT11863C

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