Abstract
The crystal structures of the compounds tris(para-chlorophenyl)phosphine oxide {(p-ClPh)3PO} and tris(para-methoxyphenyl)phosphine oxide {(p-OMePh)3PO} were determined by X-ray diffraction methods. (p-ClPh)3PO crystallizes in the space group P-1 (no. 2) with a = 11.828(2), b = 12.645(2), c = 14.072(2) Å, α = 97.90(1), β = 109.45(1), γ = 115.43(1), V = 1692.3(2) Å3 and Z = 4. The mean O–P and C–P distances are 1.481(6) and 1.806(2) Å, respectively, and the mean C–P–C angle is 106.5(1.1). (p-OMePh)3PO crystallizes in the space group P21/c (no. 14) with a = 18.8642 (10), b = 10.3999(5), c = 21.3462(16) Å, β = 115.414(6)°, V= 3782.6(4) Å3, and Z = 8. The mean O–P and C–P distances are 1.484(5) and 1.798(4) Å, respectively, and the mean C–P–C angle is 106.5(1.0). These two structures were analyzed along with the previously determined structures of triphenylphosphine oxide {Ph3PO} and tri-p-tolylphosphine oxide {(p-MePh)3PO}, and IR data were collected on all four compounds. Both the observed P–O distances and the IR stretching frequencies for these triarylphosphine oxides support the interpretation of the P–O bond as having substantial multiple-bond character, with a bond order between 1.7 and 1.8. The para-substituents on these triarylphosphines were shown to have a statistically insignificant effect on the P–O bond.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Gilheany, D.G. Chem. Rev. 1994, 94, 1339.
Messmer, R.P. J. Am. Chem. Soc. 1991, 113, 433.
Reed, A.E., Schleyer, P.v.R. J. Am. Chem. Soc. 1990, 112, 1434.
Schmidt, M.W., Gordon, M.S. J. Am. Chem. Soc. 1985, 107, 1922.
Kutzelnigg, W. Angew. Chem. Int. Ed. Engl. 1984, 23, 272.
Grein, F., Lawlor, L.J. Theor. Chim. Acta. 1983, 63, 161.
Xiao, S.-X., Trogler, W.C., Ellis, D.E., Berkovitch-Yellin, Z. J. Am. Chem. Soc. 1983, 105, 7033.
Pietro, W.J., Francl, M.M., Hehre, W.J., DeFrees, D.J., Pople, J.A., Binkley, J.S. J. Am. Chem. Soc. 1982, 104, 5039.
Pauling, L. The Nature of the Chemical Bond, 3rd ed.; Cornell University Press: Ithaca, NY, 1960.
O'Keeffe, M.; Brese, N.E. J. Am. Chem. Soc. 1991, 113, 3226.
Churchill, M.R.; See, R.F., Randall, S.L.; Atwood, J.D. Acta Crystallogr. 1993, C49, 345.
Spek, A.L. Acta Crystallogr. 1987, C43, 1233.
Dunne, B.J., Morris, R.B., Orpen, A.G. J. Chem. Soc. Dalton Trans. 1991, 653.
Orpen, A.G., Connelly, N.G. Organometallics 1990, 9, 1206.
XSCANS Software Users Guide, Version 2.1; Siemens Industrial Automation, Inc.; Madison, WI, 1994.
Broach, R.W. Argonne National Laboratory: Illinois, 1978.
Engelhardt, L.M., Raston, C.L., Whitaker, C.R., White, A.H. Aust. J. Chem. 1986, 39, 2151.
Bell, J.V.; Heisler, J.; Tannenbaum, H.; Goldenson, J. J. Am. Chem. Soc. 1954, 76, 5185.
Lynch, V.M., Kampa, J.J., Lagow, R.J., Davis, B.E. Acta Crystallogr. 1993, C49, 1549.
Allen, F.H., Kennard, O., Watson, D.G., Brammer, L., Orpen, A.G., Taylor, R. J. Chem. Soc. Perkin Trans. II 1987, S1–19.
Urusov, V.S. Acta. Crystallogr. 1995, B51, 641.
Burdett, J.K., Hawthorne, F.C. Am. Mineralogist 1993, 78, 884.
Brown, I.D. Acta Crystallogr. 1992, B48, 553.
Silverstein, R.M.; Bassler, G.C.; Morrill, T.C. Spectroscopic Identification of Organic Compounds, 5th ed.; John Wiley & Sons: New York, 1991.
Sheldrick, G.M. Acta Crystallogr. 1990, A46, 467–473.
Sheldrick, G.M. Shelx93 Program for Refinement of Crystal Structures, University of Göttingen: Germany, 1993.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
See, R.F., Dutoi, A.D., Fettinger, J.C. et al. The crystal structures of (p-ClPh)3PO and (p-OMePh)3PO, including an analysis of the P-O bond in triarylphosphine oxides. Journal of Chemical Crystallography 28, 893–898 (1998). https://doi.org/10.1023/A:1022850503138
Issue Date:
DOI: https://doi.org/10.1023/A:1022850503138