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Redox Chemistry of Selenenic Acids and the Insight It Brings on Transition State Geometry in the Reactions of Peroxyl Radicals

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Department of Chemistry, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada
Department of Chemistry “G. Ciamician”, University of Bologna, I-40126 Bologna, Italy
Cite this: J. Am. Chem. Soc. 2014, 136, 4, 1570–1578
Publication Date (Web):January 2, 2014
https://doi.org/10.1021/ja411493t
Copyright © 2014 American Chemical Society

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    Abstract

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    The redox chemistry of selenenic acids has been explored for the first time using a persistent selenenic acid, 9-triptyceneselenenic acid (RSeOH), and the results have been compared with those we recently obtained with its lighter chalcogen analogue, 9-triptycenesulfenic acid (RSOH). Specifically, the selenenyl radical was characterized by EPR spectroscopy and equilibrated with a phenoxyl radical of known stability in order to determine the O–H bond dissociation enthalpy of RSeOH (80.9 ± 0.8 kcal/mol): ca. 9 kcal/mol stronger than in RSOH. Kinetic measurements of the reactions of RSeOH with peroxyl radicals demonstrate that it readily undergoes H-atom transfer reactions (e.g., k = 1.7 × 105 M–1 s–1 in PhCl), which are subject to kinetic solvent effects and kinetic isotope effects similar to RSOH and other good H-atom donors. Interestingly, the rate constants for these reactions are only 18- and 5-fold smaller than those measured for RSOH in PhCl and CH3CN, respectively, despite being 9 kcal/mol less exothermic for RSeOH. IR spectroscopic studies demonstrate that RSeOH is less H-bond acidic than RSOH, accounting for these solvent effects and enabling estimates of the pKas in RSeOH and RSOH of ca. 15 and 10, respectively. Calculations suggest that the TS structures for these reactions have significant charge transfer between the chalcogen atom and the internal oxygen atom of the peroxyl radical, which is nominally better for the more polarizable selenenic acid. The higher than expected reactivity of RSeOH toward peroxyl radicals is the strongest experimental evidence to date for charge transfer/secondary orbital interactions in the reactions of peroxyl radicals with good H-atom donors.

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    NMR spectra of new compounds, representative voltammograms, Cartesian coordinates, and energies of stationary points determined by computation. This material is available free of charge via the Internet at http://pubs.acs.org.

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