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Volumn 78, Issue 3, 2013, Pages 1026-1037

Reactions of the phthalimide N-oxyl radical (PINO) with activated phenols: The contribution of π-stacking interactions to hydrogen atom transfer rates

Author keywords

[No Author keywords available]

Indexed keywords

2 ,4 ,6-TRIMETHYLPHENOL; AROMATIC RINGS; DEGREE OF CHARGE TRANSFER; DEUTERIUM KINETIC ISOTOPE EFFECT; HAMMETT CORRELATION; HYDROGEN TRANSFER; HYDROGEN-ATOM TRANSFER; LASER FLASH PHOTOLYSIS; MARCUS CROSS-RELATIONS; N-OXYL RADICALS; PHENOLIC ANTIOXIDANT; PHTHALIMIDE; RADICAL SCAVENGING; SOLVENT EFFECTS; STACKING INTERACTION; THEORETICAL CALCULATIONS;

EID: 84873392905     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo302483s     Document Type: Article
Times cited : (28)

References (115)
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    • Torres, E.; DiLabio, G. A. J. Phys. Chem. Lett. 2012, 3, 1738-1744. For tools to generate input files incorporating DCPs, see also www.ualberta.ca/ ∼gdilabio
    • (2012) J. Phys. Chem. Lett. , vol.3 , pp. 1738
    • Torres, E.1    Dilabio, G.A.2
  • 82
    • 84873400830 scopus 로고    scopus 로고
    • Over binding may occur in radical-molecule complexes due to erroneous charge transfer. In such cases, the DFT method employed wrongly predicts the singly-occupied molecular orbital (SOMO) of the radical to lie lower in energy than highest-occupied molecular orbital (HOMO) of the molecule, which results in excess charge transfer and, therefore, excess Coulomb attraction between the species (ref: in press). We verified that this erroneous over-binding is not occurring in our systems because, according to our computational approach, the PINO SOMO lies higher in energy that the HOMO of the phenols.
    • Over binding may occur in radical-molecule complexes due to erroneous charge transfer. In such cases, the DFT method employed wrongly predicts the singly-occupied molecular orbital (SOMO) of the radical to lie lower in energy than highest-occupied molecular orbital (HOMO) of the molecule, which results in excess charge transfer and, therefore, excess Coulomb attraction between the species (ref: Johnson, E. R.; Salamone, M.; Bietti, M.; DiLabio, G. A. J. Phys. Chem. A, in press). We verified that this erroneous over-binding is not occurring in our systems because, according to our computational approach, the PINO SOMO lies higher in energy that the HOMO of the phenols.
    • J. Phys. Chem. A
    • Johnson, E.R.1    Salamone, M.2    Bietti, M.3    Dilabio, G.A.4
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    • Derived from pseudo-self-exchange reactions (t BuOO•+ s BuOOH).
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    • Chenier, J.H.B.1    Howard, J.A.2
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    • Most organic HAT processes typically have |Δ S | = 0 because there is no change in the charges of the species involved and little change in their sizes
    • Evans, M. G.; Polanyi, M. Trans. Faraday Soc. 1938, 34, 11-24. Most organic HAT processes typically have |Δ S | = 0 because there is no change in the charges of the species involved and little change in their sizes
    • (1938) Trans. Faraday Soc. , vol.34 , pp. 11-24
    • Evans, M.G.1    Polanyi, M.2


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