Chlorobis(pentafluoroethyl)phosphane: Improved Synthesis and Molecular Structure in the Gas Phase

Hayes SA, Berger R, Mitzel NW, Bader J, Hoge B (2011)
Chemistry 17(14): 3968-3976.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
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Abstract / Bemerkung
(C2F5)(2)PCl is now accessible through a significantly improved synthesis protocol starting from the technical product (C2F5)(3)PF2. (C2F5)(3)PF2 was reduced in the first step with NaBH4 in a solvent-free reaction at 120 degrees C. The product, P(C2F5)(3), was treated with an excess of an aqueous sodium hydroxide solution to afford the corresponding phosphinite salt Na+ (C2F5)(2)PO- selectively under liberation of pentafluoroethane. Subsequent chlorination with PhPCl4 resulted in the selective formation of (C2F5)(2)PCl, which was isolated by fractional condensation in an overall yield of 66%. The gas electron diffraction (GED) pattern for (C2F5)(2)PCl was recorded and found to be described by a two-conformer model. A quantum chemical investigation of the potential-energy surface revealed the possible existence of many low-energy conformers, each with a number of low-frequency vibrational modes and there-fore large-amplitude motions. The conformer calculated to be most stable was also found to be most abundant by GED and comprised 61(5)% of the total. The molecular structure parameters determined by GED were in good agreement with those calculated at the MP2/TZVPP level of theory; the only significant difference was a discrepancy of about 3 degrees in the C-P-C angle, which, for the lowest-energy conformer, was refined to 98.2(4)degrees and was calculated to be 94.9 degrees.
Stichworte
molecular; structures; density functional calculations; gas electron diffraction; phosphorus; fluorine
Erscheinungsjahr
2011
Zeitschriftentitel
Chemistry
Band
17
Ausgabe
14
Seite(n)
3968-3976
ISSN
0947-6539
Page URI
https://pub.uni-bielefeld.de/record/2093757

Zitieren

Hayes SA, Berger R, Mitzel NW, Bader J, Hoge B. Chlorobis(pentafluoroethyl)phosphane: Improved Synthesis and Molecular Structure in the Gas Phase. Chemistry. 2011;17(14):3968-3976.
Hayes, S. A., Berger, R., Mitzel, N. W., Bader, J., & Hoge, B. (2011). Chlorobis(pentafluoroethyl)phosphane: Improved Synthesis and Molecular Structure in the Gas Phase. Chemistry, 17(14), 3968-3976. doi:10.1002/chem.201003048
Hayes, S. A., Berger, R., Mitzel, N. W., Bader, J., and Hoge, B. (2011). Chlorobis(pentafluoroethyl)phosphane: Improved Synthesis and Molecular Structure in the Gas Phase. Chemistry 17, 3968-3976.
Hayes, S.A., et al., 2011. Chlorobis(pentafluoroethyl)phosphane: Improved Synthesis and Molecular Structure in the Gas Phase. Chemistry, 17(14), p 3968-3976.
S.A. Hayes, et al., “Chlorobis(pentafluoroethyl)phosphane: Improved Synthesis and Molecular Structure in the Gas Phase”, Chemistry, vol. 17, 2011, pp. 3968-3976.
Hayes, S.A., Berger, R., Mitzel, N.W., Bader, J., Hoge, B.: Chlorobis(pentafluoroethyl)phosphane: Improved Synthesis and Molecular Structure in the Gas Phase. Chemistry. 17, 3968-3976 (2011).
Hayes, Stuart A., Berger, Raphael, Mitzel, Norbert W., Bader, Julia, and Hoge, Berthold. “Chlorobis(pentafluoroethyl)phosphane: Improved Synthesis and Molecular Structure in the Gas Phase”. Chemistry 17.14 (2011): 3968-3976.

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