Structural Effects on the pH-Dependent Redox Properties of Organic Nitroxyls: Pourbaix Diagrams for TEMPO, ABNO, and Three TEMPO Analogs

Gerken, James B.; Pang, Yutong Q.; Lauber, Markus B.; Stahl, Shannon S.

doi:10.1021/acs.joc.7b02547

Structural Effects on the pH-Dependent Redox Properties of Organic Nitroxyls: Pourbaix Diagrams for TEMPO, ABNO, and Three TEMPO Analogs

Journal Article · Tue Nov 28 00:00:00 EST 2017 · Journal of Organic Chemistry

DOI:https://doi.org/10.1021/acs.joc.7b02547· OSTI ID:1471688

Gerken, James B. ^[1]; Pang, Yutong Q. ^[2]; Lauber, Markus B. ^[2]; ^[2]

Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemistry; University of Wisconsin-Madison
Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemistry

Here, electrochemical studies of the reduction and oxidation reactions of five different organic nitroxyls have been performed across a wide pH range (0–13). The resulting Pourbaix diagrams illustrate structural effects on their various redox potentials and on the pK_a values of the corresponding hydroxylamine and hydroxylammonium ions. Evidence is also given for the reversible formation of a hydroxylamine N-oxide when nitroxyls are oxidized in alkaline media. Structural effects on the thermodynamics of this reaction are assessed.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME); Univ. of Wisconsin, Madison, WI (United States)

Sponsoring Organization:: National Inst. of Health (NIH); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: FC02-07ER64494

OSTI ID:: 1471688

Journal Information:: Journal of Organic Chemistry, Journal Name: Journal of Organic Chemistry Journal Issue: 14 Vol. 83; ISSN 0022-3263

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Nitroxide Chemical Reactions Likhtenshtein, Gertz I. Nitroxides: Brief History, Fundamentals, and Recent Developments, p. 35-69 https://doi.org/10.1007/978-3-030-34822-9_3	book	January 2020
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