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Issue 44, 2018
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Distinguishing ionic and radical mechanisms of hydroxylamine mediated electrocatalytic alcohol oxidation using NO–H bond dissociation energies

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Abstract

The mechanism of N-oxyl radical catalyzed oxidation is a long-standing scientific problem. In this work, radical or ionic mechanisms in electrocatalytic oxidation of alcohols are discussed on the NO–H bond dissociation energy (BDE) scale. A thermodynamic model was built to outline the range of BDEs for the catalysts that react via the two mechanisms. The N-oxyl radical catalyzed electrocatalytic benzyl alcohol oxidations with NO–H BDEs smaller than 74 kcal mol−1 reacted by an ionic mechanism, and with BDEs greater than 78 kcal mol−1 reacted by a radical mechanism. Oxidizing aliphatic alcohols via a radical mechanism requires catalysts with BDEs even greater than that of N-hydroxyphthalimide (NHPI), and the ionic mechanism requires catalysts with BDEs smaller than 74 kcal mol−1. With either the ionic or radical mechanism, catalysts with larger BDEs correspond to a smaller activation energy of the key step. Future design of N-oxyls with catalytic activity in alcohol oxidation can be streamlined by our efforts.

Graphical abstract: Distinguishing ionic and radical mechanisms of hydroxylamine mediated electrocatalytic alcohol oxidation using NO–H bond dissociation energies

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Publication details

The article was received on 01 Oct 2018, accepted on 17 Oct 2018 and first published on 18 Oct 2018


Article type: Paper
DOI: 10.1039/C8CP06134C
Citation: Phys. Chem. Chem. Phys., 2018,20, 28249-28256
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    Distinguishing ionic and radical mechanisms of hydroxylamine mediated electrocatalytic alcohol oxidation using NO–H bond dissociation energies

    R. Dao, C. Zhao, J. Yao and H. Li, Phys. Chem. Chem. Phys., 2018, 20, 28249
    DOI: 10.1039/C8CP06134C

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