Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 143, Issue 27, Pages 10324-10332Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.1c04181
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Funding
- National Science Foundation [CHE-1565782, CBET-2033714]
- University of Michigan
- Department of Energy [DE-SC0006628]
- Natural Sciences and Engineering Research Council of Canada
- Compute Ontario
- Compute Canada
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The study found that PINO can be generated from NHPI through multiple-site concerted proton-electron transfer, while its decomposition occurs through at least two paths, one of which is greatly enhanced by base. Optimal catalytic efficiency in PINO-catalyzed oxidations occurs in the presence of bases with appropriate pK(a) values.
Phthalimide N-oxyl (PINO) is a potent hydrogen atom transfer (HAT) catalyst that can be generated electrochemically from N-hydroxyphthalimide (NHPI). However, catalyst decomposition has limited its application. This paper details mechanistic studies of the generation and decomposition of PINO under electrochemical conditions. Voltammetric data, observations from bulk electrolysis, and computational studies suggest two primary aspects. First, base-promoted formation of PINO from NHPI occurs via multiple-site concerted proton-electron transfer (MS-CPET). Second, PINO decomposition occurs by at least two second-order paths, one of which is greatly enhanced by base. Optimal catalytic efficiency in PINO-catalyzed oxidations occurs in the presence of bases whose corresponding conjugate acids have pK(a)'s in the range of similar to 11-15, which strikes a balance between promoting PINO formation and minimizing its decay.
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