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Assessing the stereoelectronic properties of pyrrolyl phosphines and related ligands : the quantitative analysis of ligand effects (QALE)

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Abstract
By application of the QALE model (quantitative analysis of ligand effects) to the standard reduction potentials (E degrees values) and the standard enthalpies of reduction (Delta H degrees) of the eta-Cp(CO)(PZ(3))Fe(COMe)(+/0) couple (PZ(3)= a phosphorus(III) ligand), and nu(CO) for eta-Cp(CO)(PZ(3))Fe(COMe)(0), we have determined that a minimum of four parameters are necessary to describe the stereoelectronic properties of the set of ligands PPhi(Pyr)(3-i) (Pyr = pyrrolyl) and P(NC4H8)(3) (NC4H8=pyrrolidinyl). These parameters are chi(d), theta, E-ar and the pi acidity parameter, pi(p). The values of these parameters were determined by linear regression analysis of a set of QALE equations. The coefficients of these equations were based on the analyses of data for PR3, PPhiR3-i, P(p-XC6H4)(3), P(OR)(3), and P(O-p-XC6H4)(3). The parameters for P(Pyr)(3) are chi(d)=31.9 +/- 0.7, theta=145 +/- 3, E-ar=3.3 +/- 0.2 and pi(p)=1.9 +/- 0.2; and for P(NC4H8)(3) the parameters are chi(d)=-1.2 +/- 1.4, theta=145 +/- 5, E-ar=-0.6 +/- 0.4 and pi(p)=0.9 +/- 0.3. P(Pyr)(3) is a poor sigma donor that possesses an E-ar parameter comparable to P(p-XC6H4)(3) and a pi acidity that is about two thirds that of P(OR)(3) and half that of P(O-p-XC6H4)(3). On the other hand, P(NC4H8)(3), which is one of the strongest sigma donor phosphorus(III) ligands, is a weak pi acid with a value for E-ar that is statistically indistinguishable from zero. PPhi(Pyr)(3-i) and P(NC4H8)(3) appear to be isosteric to P(p-XC6H4)(3).
Keywords
ENTHALPY-ENTROPY RELATIONSHIP, METAL-CARBONYL CLUSTERS, UNIMOLECULAR REACTION SYSTEMS, STATISTICAL-MECHANICAL MODEL, PI-ACCEPTOR CHARACTER, ISOKINETIC RELATIONSHIP, SUBSTITUTION-REACTIONS, EXPLORING STEREOSELECTIVITY, PHOSPHORUS(III) LIGANDS, L(2)FE(CO)(3) SYSTEM

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MLA
Fernandez, A., et al. “Assessing the Stereoelectronic Properties of Pyrrolyl Phosphines and Related Ligands : The Quantitative Analysis of Ligand Effects (QALE).” JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, no. 7, 2000, pp. 1349–57.
APA
Fernandez, A., Reyes, C., Lee, T., Prock, A., Giering, W., Haar, C., & Nolan, S. (2000). Assessing the stereoelectronic properties of pyrrolyl phosphines and related ligands : the quantitative analysis of ligand effects (QALE). JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, (7), 1349–1357.
Chicago author-date
Fernandez, A, C Reyes, TY Lee, A Prock, WP Giering, CM Haar, and Steven Nolan. 2000. “Assessing the Stereoelectronic Properties of Pyrrolyl Phosphines and Related Ligands : The Quantitative Analysis of Ligand Effects (QALE).” JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, no. 7: 1349–57.
Chicago author-date (all authors)
Fernandez, A, C Reyes, TY Lee, A Prock, WP Giering, CM Haar, and Steven Nolan. 2000. “Assessing the Stereoelectronic Properties of Pyrrolyl Phosphines and Related Ligands : The Quantitative Analysis of Ligand Effects (QALE).” JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2 (7): 1349–1357.
Vancouver
1.
Fernandez A, Reyes C, Lee T, Prock A, Giering W, Haar C, et al. Assessing the stereoelectronic properties of pyrrolyl phosphines and related ligands : the quantitative analysis of ligand effects (QALE). JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2. 2000;(7):1349–57.
IEEE
[1]
A. Fernandez et al., “Assessing the stereoelectronic properties of pyrrolyl phosphines and related ligands : the quantitative analysis of ligand effects (QALE),” JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, no. 7, pp. 1349–1357, 2000.
@article{8170854,
  abstract     = {By application of the QALE model (quantitative analysis of ligand effects) to the standard reduction potentials (E degrees values) and the standard enthalpies of reduction (Delta H degrees) of the eta-Cp(CO)(PZ(3))Fe(COMe)(+/0) couple (PZ(3)= a phosphorus(III) ligand), and nu(CO) for eta-Cp(CO)(PZ(3))Fe(COMe)(0), we have determined that a minimum of four parameters are necessary to describe the stereoelectronic properties of the set of ligands PPhi(Pyr)(3-i) (Pyr = pyrrolyl) and P(NC4H8)(3) (NC4H8=pyrrolidinyl). These parameters are chi(d), theta, E-ar and the pi acidity parameter, pi(p). The values of these parameters were determined by linear regression analysis of a set of QALE equations. The coefficients of these equations were based on the analyses of data for PR3, PPhiR3-i, P(p-XC6H4)(3), P(OR)(3), and P(O-p-XC6H4)(3). The parameters for P(Pyr)(3) are chi(d)=31.9 +/- 0.7, theta=145 +/- 3, E-ar=3.3 +/- 0.2 and pi(p)=1.9 +/- 0.2; and for P(NC4H8)(3) the parameters are chi(d)=-1.2 +/- 1.4, theta=145 +/- 5, E-ar=-0.6 +/- 0.4 and pi(p)=0.9 +/- 0.3. P(Pyr)(3) is a poor sigma donor that possesses an E-ar parameter comparable to P(p-XC6H4)(3) and a pi acidity that is about two thirds that of P(OR)(3) and half that of P(O-p-XC6H4)(3). On the other hand, P(NC4H8)(3), which is one of the strongest sigma donor phosphorus(III) ligands, is a weak pi acid with a value for E-ar that is statistically indistinguishable from zero. PPhi(Pyr)(3-i) and P(NC4H8)(3) appear to be isosteric to P(p-XC6H4)(3).},
  author       = {Fernandez, A and Reyes, C and Lee, TY and Prock, A and Giering, WP and Haar, CM and Nolan, Steven},
  issn         = {1470-1820},
  journal      = {JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2},
  keywords     = {ENTHALPY-ENTROPY RELATIONSHIP,METAL-CARBONYL CLUSTERS,UNIMOLECULAR REACTION SYSTEMS,STATISTICAL-MECHANICAL MODEL,PI-ACCEPTOR CHARACTER,ISOKINETIC RELATIONSHIP,SUBSTITUTION-REACTIONS,EXPLORING STEREOSELECTIVITY,PHOSPHORUS(III) LIGANDS,L(2)FE(CO)(3) SYSTEM},
  language     = {eng},
  number       = {7},
  pages        = {1349--1357},
  title        = {Assessing the stereoelectronic properties of pyrrolyl phosphines and related ligands : the quantitative analysis of ligand effects (QALE)},
  url          = {http://dx.doi.org/10.1039/b003494k},
  year         = {2000},
}

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