Accurate O−H bond dissociation energy differences of hydroxylamines determined by EPR Spectroscopy: computational insight into stereoelectronic effects on BDEs and EPR spectral parameters

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DOIResolve DOI: http://doi.org/10.1021/jo1021794
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TypeArticle
Journal titleThe Journal of Organic Chemistry
Volume76
Issue2
Pages631636; # of pages: 6
AbstractDifferences in O−H bond dissociation enthalpies (ΔBDEs) between the hydroxylamine of 15N-labeled TEMPONE and 10 N,N-di-tert-alkyl hydroxylamines were determined by EPR. These ΔBDEs, together with the g and aN values of the derived nitroxide radicals, are discussed in relation to various geometric, intramolecular dipole/dipole, and steric effects and in relation to the results from DFT calculations. We find that dipole/dipole interactions are the dominant factors in dictating aN values and O−H BDEs in all of these structurally similar nitroxides and hydroxylamines, respectively. The importance of including the Boltzmann distribution of conformations for each nitroxide in the aN calculations is emphasized.
Publication date
LanguageEnglish
AffiliationNational Institute for Nanotechnology; NRC Steacie Institute for Molecular Sciences; National Research Council Canada
Peer reviewedYes
NPARC number19739661
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Record identifierf935bff7-76d4-498c-8cff-27f029fe69be
Record created2012-04-02
Record modified2016-05-09
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