A theoretical study of the iminoxyl/oxime self-exchange reaction. A five-center, cyclic proton-coupled electron transfer

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DOIResolve DOI: http://doi.org/10.1021/ja0500409
AuthorSearch for: ; Search for:
TypeArticle
Journal titleJACS: Journal of the American Chemical Society
ISSN0002-7863
Volume127
Issue18
Pages66936699; # of pages: 7
AbstractIn solution, the self-exchange reactions for oxygen-centered π-radicals, e.g., PhO⋅ + PhOH ⇌ PhOH + PhO⋅, are known to occur with low activation enthalpies (Ea ≈ 2 kcal/mol). For the PhO⋅/PhOH couple and, we conclude, for other O-centered π-radicals, exchange occurs by proton-coupled electron transfer (PCET) with the proton transferred between oxygen electron pairs while the electron migrates between oxygen orbitals orthogonal to the -O- - -H- - -O- transition state plane (Mayer et al. J. Am. Chem. Soc. 2002, 123, 11142). Iminoxyls, R₂C=NO⋅, are σ-radicals with substantial spin density on the nitrogen. The R₂C=NO⋅/R₂C=NOH self-exchange has a significant Ea (Mendenhall et al. J. Am. Chem. Soc. 1973, 95, 627). For this exchange, DFT calculations have revealed a counterintuitive cisoid transition state in which the seven atoms, >C=NO- - -H- - -ON=C<, lie in a plane (R = H, Me) or, for steric reasons, two planes twisted at 45.2° (R = Me₃C). The planar transition state has the two N-O dipoles close to each other and pointing in the same direction and an O- - -H- - -O angle of 165.4°. A transoid transition state for R = H lies 3.4 kcal/mol higher in energy than the cisoid despite a more favorable arrangement of the dipoles and a near linear O- - -H- - -O. It is concluded that iminoxyl/oxime self-exchange reactions occur by a five-center, cyclic PCET mechanism with the proton being transferred between electron pairs on the oxygens and the electron migrating between in-plane orbitals on the two nitrogens (RN-N = 2.65 Å). The calculated Ea values (8.8-9.9 kcal/mol) are in satisfactory agreement with the limited experimental data.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada; National Institute for Nanotechnology; NRC Steacie Institute for Molecular Sciences
Peer reviewedYes
Identifier10072378
NRC number73
NPARC number12329149
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Record identifier8392a607-c9d6-48a2-924b-68964df8f38e
Record created2009-09-10
Record modified2016-05-09
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