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Alkyl radical adducts of aromatic N-oxides as hydrogen-abstracting agents: The reactivity of phenazine-N,N′-dioxide-methyl radical adduct

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Abstract

An O-methylated analog of protonated phenazine-di-N-oxide radical anion abstracts hydrogen from primary and secondary alcohols in a slow (k 1 < 500 M−1 s−1) bimolecular reaction. No kinetic evidence has been found for the unimolecular release of free methoxyl radicals through the homolytic N-OMe bond cleavage in these species. DFT calculations at the UB3LYP 6-31G(d) level indicate that protonated and O-alkylated radical anions of pyrazine, quinoxaline and phenazine di-N-oxides are close analogues of aromatic nitroxyl radicals with the highest spin density localized on the oxygen and nitrogen of the nitrone moiety.

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Authors and Affiliations

  1. Department of Physics, Astronomy and Geology, East Tennessee State University, Box 70652, Johnson City, TN, 37614, USA

    Yuriy Razskazovskiy & David M. Close

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  1. Yuriy Razskazovskiy
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  2. David M. Close
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Correspondence to Yuriy Razskazovskiy.

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Razskazovskiy, Y., Close, D.M. Alkyl radical adducts of aromatic N-oxides as hydrogen-abstracting agents: The reactivity of phenazine-N,N′-dioxide-methyl radical adduct. Res Chem Intermed 32, 625–635 (2006). https://doi.org/10.1163/156856706778400325

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  • DOI: https://doi.org/10.1163/156856706778400325

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