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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Download	View accepted manuscript: Accurate O−H bond dissociation energy differences of hydroxylamines determined by EPR Spectroscopy: computational insight into stereoelectronic effects on BDEs and EPR spectral parameters (PDF, 869 KiB)
DOI	Resolve DOI: https://doi.org/10.1021/jo1021794
Author	Search for: Billone, Paul S.; Search for: Johnson, Paul A.¹; Search for: Lin, Shuqiong²; Search for: Scaiano, J. C.; Search for: DiLabio, Gino A.¹; Search for: Ingold, K. U.²
Affiliation	National Research Council of Canada. National Institute for Nanotechnology National Research Council of Canada. NRC Steacie Institute for Molecular Sciences
Format	Text, Article
Abstract	Differences 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	2010-12-23
In	The Journal of Organic Chemistry 76, no. 2 (23 December 2010): 631–636.
Language	English
Peer reviewed	Yes
NPARC number	19739661
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Record identifier	f935bff7-76d4-498c-8cff-27f029fe69be
Record created	2012-04-02
Record modified	2020-04-17

Date modified:: 2024-07-19