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Conformations of organophosphine oxides

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
 [1];  [1];  [2];  [1];  [1]
  1. Iowa State Univ., Ames, IA (United States); Ames Lab., Ames, IA (United States)
  2. Supramolecular Design Inst., Oak Ridge, TN (United States)
+ Show Author Affiliations
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.
Research Organization:
Ames Laboratory (AMES), Ames, IA (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Organization:
DOE Office of Science; USDOE
Grant/Contract Number:
AC02-07CH11358
OSTI ID:
1227401
Report Number(s):
IS-J--8636
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 32 Vol. 119; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (4)

The Impact of Crystal Packing and Aurophilic Interactions on the Luminescence Properties in Polymorphs and Solvate of Aroylacetylide–Gold(I) Complexes journal August 2019
Disentangling different modes of mobility for triphenylphosphine oxide adsorbed on alumina journal February 2020
Triethylphosphine as a molecular gear — phase transitions in ferrocenyl–acetylide–gold(I) journal August 2018
Triethylphosphine as a molecular gear – phase transitions in ferrocenyl–acetylide–gold(I) journal August 2019

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