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

Abstract

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 pKa 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.

Authors:
 [1];  [1];  [1]; ORCiD logo [1]
  1. Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME); Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); National Institutes of Health (NIH)
OSTI Identifier:
1471688
Grant/Contract Number:  
FC02-07ER64494; CHE-9208463; S10 RR08389
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Organic Chemistry
Additional Journal Information:
Journal Volume: 83; Journal Issue: 14; Journal ID: ISSN 0022-3263
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Gerken, James B., Pang, Yutong Q., Lauber, Markus B., and Stahl, Shannon S. Structural Effects on the pH-Dependent Redox Properties of Organic Nitroxyls: Pourbaix Diagrams for TEMPO, ABNO, and Three TEMPO Analogs. United States: N. p., 2017. Web. doi:10.1021/acs.joc.7b02547.
Gerken, James B., Pang, Yutong Q., Lauber, Markus B., & Stahl, Shannon S. Structural Effects on the pH-Dependent Redox Properties of Organic Nitroxyls: Pourbaix Diagrams for TEMPO, ABNO, and Three TEMPO Analogs. United States. https://doi.org/10.1021/acs.joc.7b02547
Gerken, James B., Pang, Yutong Q., Lauber, Markus B., and Stahl, Shannon S. Tue . "Structural Effects on the pH-Dependent Redox Properties of Organic Nitroxyls: Pourbaix Diagrams for TEMPO, ABNO, and Three TEMPO Analogs". United States. https://doi.org/10.1021/acs.joc.7b02547. https://www.osti.gov/servlets/purl/1471688.
@article{osti_1471688,
title = {Structural Effects on the pH-Dependent Redox Properties of Organic Nitroxyls: Pourbaix Diagrams for TEMPO, ABNO, and Three TEMPO Analogs},
author = {Gerken, James B. and Pang, Yutong Q. and Lauber, Markus B. and Stahl, Shannon S.},
abstractNote = {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 pKa 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.},
doi = {10.1021/acs.joc.7b02547},
journal = {Journal of Organic Chemistry},
number = 14,
volume = 83,
place = {United States},
year = {2017},
month = {11}
}

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Works referencing / citing this record:

Nitroxide Chemical Reactions
book, January 2020


Electrochemical TEMPO-catalyzed multicomponent C(sp 3 )–H α-carbamoylation of free cyclic secondary amines
journal, January 2019

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Electrochemical Performance of ABNO for Oxidation of Secondary Alcohols in Acetonitrile Solution
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