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A thermodynamic method based on isoequilibrium behavior to determine the values of stereoelectronic parameters of phosphines

Author
Organization
Abstract
Isoequilibrium behavior provides a method of determining stereoelectronic parameters, for use in linear free energy relationships. This method is based on thermodynamics and is different from the usual ways of assigning values to these parameters. Analysis of isoequilibrium behavior is done in terms of the three parameter QALE (quantitative analysis of ligand effects) model, with parameters chi, theta and E-ar. We use this method to interpret new E degrees/T values of the eta-Cp(CO)(L)Fe(COMe)(+/0) couple (Cp = cyclopentadienyl, L = PPhiR3-i) and established way to calculate chi and E-ar values for PPhiR3-i. In support of the validity of the method, we find that these calculated chi values agree well, except for PPh2Pri, with the values previously reported by Bartik. We also calculated a value for chi equal to 0.4 for P(NC4H8)(3) for which a chi value had not been reported previously.
Keywords
LIGAND EFFECTS QALE, ENTHALPY-ENTROPY RELATIONSHIP, METAL-CARBONYL CLUSTERS, UNIMOLECULAR REACTION SYSTEMS, STATISTICAL-MECHANICAL MODEL, P-DONOR NUCLEOPHILES, ISOKINETIC RELATIONSHIP, QUANTITATIVE-ANALYSIS, EXPLORING STEREOSELECTIVITY, ORGANOMETALLIC CHEMISTRY

Citation

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MLA
Fernandez, AL, et al. “A Thermodynamic Method Based on Isoequilibrium Behavior to Determine the Values of Stereoelectronic Parameters of Phosphines.” JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, no. 11, 1999, pp. 2631–39.
APA
Fernandez, A., Lee, T., Reyes, C., Prock, A., Giering, W., Haar, C., & Nolan, S. (1999). A thermodynamic method based on isoequilibrium behavior to determine the values of stereoelectronic parameters of phosphines. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, (11), 2631–2639.
Chicago author-date
Fernandez, AL, TY Lee, C Reyes, A Prock, WP Giering, CM Haar, and Steven Nolan. 1999. “A Thermodynamic Method Based on Isoequilibrium Behavior to Determine the Values of Stereoelectronic Parameters of Phosphines.” JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, no. 11: 2631–39.
Chicago author-date (all authors)
Fernandez, AL, TY Lee, C Reyes, A Prock, WP Giering, CM Haar, and Steven Nolan. 1999. “A Thermodynamic Method Based on Isoequilibrium Behavior to Determine the Values of Stereoelectronic Parameters of Phosphines.” JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2 (11): 2631–2639.
Vancouver
1.
Fernandez A, Lee T, Reyes C, Prock A, Giering W, Haar C, et al. A thermodynamic method based on isoequilibrium behavior to determine the values of stereoelectronic parameters of phosphines. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2. 1999;(11):2631–9.
IEEE
[1]
A. Fernandez et al., “A thermodynamic method based on isoequilibrium behavior to determine the values of stereoelectronic parameters of phosphines,” JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, no. 11, pp. 2631–2639, 1999.
@article{8170892,
  abstract     = {Isoequilibrium behavior provides a method of determining stereoelectronic parameters, for use in linear free energy relationships. This method is based on thermodynamics and is different from the usual ways of assigning values to these parameters. Analysis of isoequilibrium behavior is done in terms of the three parameter QALE (quantitative analysis of ligand effects) model, with parameters chi, theta and E-ar. We use this method to interpret new E degrees/T values of the eta-Cp(CO)(L)Fe(COMe)(+/0) couple (Cp = cyclopentadienyl, L = PPhiR3-i) and established way to calculate chi and E-ar values for PPhiR3-i. In support of the validity of the method, we find that these calculated chi values agree well, except for PPh2Pri, with the values previously reported by Bartik. We also calculated a value for chi equal to 0.4 for P(NC4H8)(3) for which a chi value had not been reported previously.},
  author       = {Fernandez, AL and Lee, TY and Reyes, C and Prock, A and Giering, WP and Haar, CM and Nolan, Steven},
  issn         = {0300-9580},
  journal      = {JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2},
  keywords     = {LIGAND EFFECTS QALE,ENTHALPY-ENTROPY RELATIONSHIP,METAL-CARBONYL CLUSTERS,UNIMOLECULAR REACTION SYSTEMS,STATISTICAL-MECHANICAL MODEL,P-DONOR NUCLEOPHILES,ISOKINETIC RELATIONSHIP,QUANTITATIVE-ANALYSIS,EXPLORING STEREOSELECTIVITY,ORGANOMETALLIC CHEMISTRY},
  language     = {eng},
  number       = {11},
  pages        = {2631--2639},
  title        = {A thermodynamic method based on isoequilibrium behavior to determine the values of stereoelectronic parameters of phosphines},
  url          = {http://dx.doi.org/10.1039/a902298h},
  year         = {1999},
}

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