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Phosphine oxide

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Phosphine oxide
Identifiers
3D model (JSmol)
  • InChI=1S/H3OP/c1-2/h2H3
    Key: MPQXHAGKBWFSNV-UHFFFAOYSA-N
  • [O-][PH3+]
Properties
H3OP
Molar mass 49.997 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Phosphine oxide is the inorganic compound with the formula H3PO. Although stable as a dilute gas, liquid or solid samples are unstable. Unlike many other compounds of the type POxHy, H3PO is rarely discussed and is not even mentioned in major sources on main group chemistry.[1]

H3PO has been detected by mass spectrometry as a reaction product of oxygen and phosphine,[2] by means of FT-IR in a phosphine-ozone reaction[3]

Generation

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Phosphine oxide has been claimed as the product of a reaction of phosphine with vanadium oxytrichloride as well as with chromyl chloride. The product was obtained by matrix isolation.[4] It has also been reported relatively stable in a water-ethanol solution by electrochemical oxidation of white phosphorus, where it slowly disproportionates into phosphine and hypophosphorous acid.[5]

Phosphine oxide is reported as an intermediate in the room-temperature polymerization of phosphine and nitric oxide to solid PxHy.[6]

Further reading

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  • Chesnut, D. B.; Savin, A. (1999). "The Electron Localization Function (ELF) Description of the PO Bond in Phosphine Oxide". Journal of the American Chemical Society. 121 (10): 2335–2336. doi:10.1021/ja984314m.
  • Alkorta, Ibon; Sánchez-Sanz, Goar; Elguero, José; Del Bene, Janet E. (2014). "Pnicogen Bonds between X═PH3 (X = O, S, NH, CH2) and Phosphorus and Nitrogen Bases". The Journal of Physical Chemistry A. 118 (8): 1527–1537. Bibcode:2014JPCA..118.1527A. doi:10.1021/jp411623h. PMID 24547683.

References

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  1. ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
  2. ^ Hamilton, Peter A.; Murrells, Timothy P. (1985). "Kinetics and mechanism of the reactions of PH3 with O(3P) and N(4S) atoms". J. Chem. Soc., Faraday Trans. 2 (81): 1531–1541. doi:10.1039/F29858101531.
  3. ^ Withnall, Robert; Andrews, Lester (1987). "FTIR spectra of the photolysis products of the phosphine-ozone complex in solid argon". J. Phys. Chem. 91 (4): 784–797. doi:10.1021/j100288a008.
  4. ^ Kayser, David A.; Ault, Bruce S. (2003). "Matrix Isolation and Theoretical Study of the Photochemical Reaction of PH3 with OVCl3 and CrCl2O2". J. Phys. Chem. A. 107 (33): 6500–6505. Bibcode:2003JPCA..107.6500K. doi:10.1021/jp022692e.
  5. ^ Yakhvarov, D.; Caporali, M.; Gonsalvi, L.; Latypov, S.; Mirabello, V.; Rizvanov, I.; Sinyashin, O.; Stoppioni, P.; Peruzzini, M. (2011). "Experimental Evidence of Phosphine Oxide Generation in Solution and Trapping by Ruthenium Complexes". Angewandte Chemie International Edition. 50 (23): 5370–5373. doi:10.1002/anie.201100822. PMID 21538749.
  6. ^ Zhao, Yi-Lei; Flora, Jason W.; David Thweatt, William; Garrison, Stephen L.; Gonzalez, Carlos; Houk, K. N.; Marquez, Manuel (2009). "Phosphine Polymerization by Nitric Oxide: Experimental Characterization and Theoretical Predictions of Mechanism". Inorg. Chem. 48 (3): 1223–1231. doi:10.1021/ic801917a. PMID 19102679.