Conformations of organophosphine oxides
Abstract
The conformations of a series of organophosphine oxides, OP(CH3)2R, where R = methyl, ethyl, isopropyl, tert-butyl, vinyl, and phenyl, are predicted using the MP2/cc-pVTZ level of theory. Comparison of potential energy surfaces for rotation about P–C bonds with crystal structure data reveals a strong correlation between predicted location and energetics of minima and histograms of dihedral angle distributions observed in the solid state. In addition, the most stable conformers are those that minimize the extent of steric repulsion between adjacent rotor substituents, and the torsional barriers tend to increase with the steric bulk of the rotating alkyl group. MM3 force field parameters were adjusted to fit the MP2 results, providing a fast and accurate model for predicting organophosphine oxides shapes—an essential part of understanding the chemistry of these compounds. As a result, the predictive power of the modified MM3 model was tested against MP2/cc-pVTZ conformations for triethylphosphine oxide, OP(CH2CH3)3, and triphenylphosphine oxide, OP(Ph)3.
- Authors:
-
- Iowa State Univ., Ames, IA (United States); Ames Lab., Ames, IA (United States)
- Supramolecular Design Inst., Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Ames Laboratory (AMES), Ames, IA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1227401
- Report Number(s):
- IS-J-8636
Journal ID: ISSN 1089-5639; TRN: US1600376
- Grant/Contract Number:
- AC02-07CH11358
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
- Additional Journal Information:
- Journal Volume: 119; Journal Issue: 32; Journal ID: ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 74 ATOMIC AND MOLECULAR PHYSICS
Citation Formats
De Silva, Nuwan, Zahariev, Federico, Hay, Benjamin P., Gordon, Mark S., and Windus, Theresa L. Conformations of organophosphine oxides. United States: N. p., 2015.
Web. doi:10.1021/acs.jpca.5b04687.
De Silva, Nuwan, Zahariev, Federico, Hay, Benjamin P., Gordon, Mark S., & Windus, Theresa L. Conformations of organophosphine oxides. United States. https://doi.org/10.1021/acs.jpca.5b04687
De Silva, Nuwan, Zahariev, Federico, Hay, Benjamin P., Gordon, Mark S., and Windus, Theresa L. Fri .
"Conformations of organophosphine oxides". United States. https://doi.org/10.1021/acs.jpca.5b04687. https://www.osti.gov/servlets/purl/1227401.
@article{osti_1227401,
title = {Conformations of organophosphine oxides},
author = {De Silva, Nuwan and Zahariev, Federico and Hay, Benjamin P. and Gordon, Mark S. and Windus, Theresa L.},
abstractNote = {The conformations of a series of organophosphine oxides, OP(CH3)2R, where R = methyl, ethyl, isopropyl, tert-butyl, vinyl, and phenyl, are predicted using the MP2/cc-pVTZ level of theory. Comparison of potential energy surfaces for rotation about P–C bonds with crystal structure data reveals a strong correlation between predicted location and energetics of minima and histograms of dihedral angle distributions observed in the solid state. In addition, the most stable conformers are those that minimize the extent of steric repulsion between adjacent rotor substituents, and the torsional barriers tend to increase with the steric bulk of the rotating alkyl group. MM3 force field parameters were adjusted to fit the MP2 results, providing a fast and accurate model for predicting organophosphine oxides shapes—an essential part of understanding the chemistry of these compounds. As a result, the predictive power of the modified MM3 model was tested against MP2/cc-pVTZ conformations for triethylphosphine oxide, OP(CH2CH3)3, and triphenylphosphine oxide, OP(Ph)3.},
doi = {10.1021/acs.jpca.5b04687},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 32,
volume = 119,
place = {United States},
year = {Fri Jul 17 00:00:00 EDT 2015},
month = {Fri Jul 17 00:00:00 EDT 2015}
}
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Works referencing / citing this record:
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