skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: 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:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC02-07CH11358
OSTI ID:
1227401
Report Number(s):
IS-J-8636; TRN: US1600376
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 119, Issue 32; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science

References (45)

Electronic structure of the phosphoryl and thiophosphoryl bonds journal April 1985
The Electron Localization Function (ELF) Description of the PO Bond in Phosphine Oxide journal March 1999
Atoms-in-Molecules and Electron Localization Function Study of the Phosphoryl Bond journal May 2003
Extraction and Separation of Neptunium, Uranium, Thorium and Cerium with TOPO from Mixed Solvents journal August 1976
Carrier-mediated transport of rare earth elements through liquid membranes. Transport of Sc, Y, Ce, Eu, Gd, Tm, Yb through supported liquid membrane containing TOPO in n-dodecane journal June 1992
Paraffin wax - Topo, an Extract ant for Actinides and Lanthanides journal May 1998
Extraction of Lanthanides(III) from Aqueous Nitrate Media with Tetra‐( p‐tolyl )[( o ‐Phenylene)Oxymethylene] Diphosphine Dioxide journal July 2009
Partitioning of actinides from high-level liquid waste employing supported liquid membrane technique using TOPO in n -dodecane as carrier journal July 2013
A critical review on solvent extraction of rare earths from aqueous solutions journal February 2014
Influence of the ionic liquid cation on the solvent extraction of trivalent rare-earth ions by mixtures of Cyanex 923 and ionic liquids journal January 2015
Solvent extraction and recovery of ethanol from aqueous solutions journal July 1988
A Liquid Phosphine Oxide: Solvent Extraction of Phenol, Acetic acid and Ethanol journal January 1988
Recovery of Uranium from Wet Phosphoric Acid by Solvent Extraction Processes journal November 2014
A Review of the Industrial and Recent Potential Applications of Trioctylphosphine Oxide journal December 1992
Acetyl-containing phosphine oxides as extractants for actinides and lanthanides journal February 2012
Actinides Extractability Trends for Multidentate Diamides and Phosphine Oxides journal January 2012
Pillar[5]arene-based phosphine oxides: novel ionophores for solvent extraction separation of f-block elements from acidic media journal January 2013
Effect of the structure of calix[4]arenes, containing phosphine oxide and phosphoryl groups and impregnated on silica gel, on the efficiency of Eu3+ extraction from aqueous solutions journal July 2013
Synthesis and Lanthanide Coordination Chemistry of Phosphine Oxide Decorated Dibenzothiophene and Dibenzothiophene Sulfone Platforms journal May 2014
Chemoenzymatic synthesis of a mixed phosphine–phosphine oxide catalyst and its application to asymmetric allylation of aldehydes and hydrogenation of alkenes journal January 2012
Synthesis of axially chiral C10-BridgePHOS oxides and their use as organocatalysts in enantioselective allylations of aldehydes journal September 2013
Enantioselective Double Aldol Reactions Involving the Sequential Activation of Silicon Tetrachloride by Chiral Phosphine Oxides journal January 2014
The preparation of bi-functional organophosphine oxides as potential antitumor agents journal November 2010
Phosphine oxide derivatives for organic light emitting diodes journal January 2012
A multifunctional phosphine oxide–diphenylamine hybrid compound as a high performance deep-blue fluorescent emitter and green phosphorescent host journal January 2014
Phosphine oxide functionalized pyrenes as efficient blue light emitting multifunctional materials for organic light emitting diodes journal January 2015
Note on an Approximation Treatment for Many-Electron Systems journal October 1934
Theoretical conformational analysis of organic molecules journal October 1974
Automated flexible ligand docking method and its application for database search journal November 1997
New Methodologies for Ligand-Based Virtual Screening journal April 2005
Search for Improved Host Architectures:  Application of de Novo Structure-Based Design and High-Throughput Screening Methods To Identify Optimal Building Blocks for Multidentate Ethers journal December 2005
De Novo Structure-Based Design of Bisurea Hosts for Tetrahedral Oxoanion Guests journal February 2006
Molecular mechanics. The MM3 force field for hydrocarbons. 1 journal November 1989
A comparison of conformational energies calculated by several molecular mechanics methods journal March 1996
Molecular Mechanics (MM3) Calculations on Oxygen-Containing Phosphorus (Coordination IV) Compounds journal July 1999
Hartree−Fock and Møller−Plesset (MP2) Treatment of Oxygen-Containing Phosphorus Compounds journal July 1997
General atomic and molecular electronic structure system journal November 1993
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
Energy-directed tree search: an efficient systematic algorithm for finding the lowest energy conformation of molecules journal January 2007
The extended Perdew-Burke-Ernzerhof functional with improved accuracy for thermodynamic and electronic properties of molecular systems journal September 2004
The Cambridge Structural Database: a quarter of a million crystal structures and rising journal May 2002
Merck molecular force field. V. Extension of MMFF94 using experimental data, additional computational data, and empirical rules journal April 1996
Merck molecular force field. III. Molecular geometries and vibrational frequencies for MMFF94 journal April 1996
MMFF VII. Characterization of MMFF94, MMFF94s, and other widely available force fields for conformational energies and for intermolecular-interaction energies and geometries This article includes Supplementary Material available from the author upon request or via the Internet at ftp.wiley.com/public/journals/jcc/suppmat/20/730 or http://journals.wiley.com/jcc/ journal May 1999
Triphenylphosphine oxide as a crystallization aid journal January 1988

Cited By (4)

Triethylphosphine as a molecular gear — phase transitions in ferrocenyl–acetylide–gold(I) journal August 2018
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 2019

Similar Records

Conformational Preferences and Internal Rotation in Alkyl- and Phenyl-Substituted Thiourea Derivatives
Journal Article · Thu Apr 13 00:00:00 EDT 2006 · Journal of Physical Chemistry A, 110(14):4678-4688 · OSTI ID:1227401
Conformational Analysis and Rotational Barriers of Alkyl- and Phenyl-Substituted Urea Derivatives
Journal Article · Thu Feb 10 00:00:00 EST 2005 · Journal of Physical Chemistry A · OSTI ID:1227401
Stereodynamics of sterically crowded metal-phosphine complexes: trans-[(t-Bu){sub 2}P(l-Pr)]{sub 2}MCl{sub 2} [M = Pt(II) and Pd(II)]. One-dimensional dynamic and two-dimensional chemical exchange NMR studies, X-ray crystallographic studies, molecular conformation trapping, and molecular mechanics calculations
Journal Article · Thu Oct 29 00:00:00 EST 1992 · Journal of Physical Chemistry · OSTI ID:1227401
+1 more

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS