Mechanism of Electrochemical Generation and Decomposition of Phthalimide-N-oxyl

被引:69
|
作者
Yang, Cheng [1 ]
Farmer, Luke A. [2 ]
Pratt, Derek A. [2 ]
Maldonado, Stephen [1 ,3 ]
Stephenson, Corey R. J. [1 ]
机构
[1] Univ Michigan, Dept Chem, Willard Henry Dow Lab, Ann Arbor, MI 48109 USA
[2] Univ Ottawa, Dept Chem & Biomol Sci, Ottawa, ON K1N 6N5, Canada
[3] Univ Michigan, Program Appl Phys, Ann Arbor, MI 48109 USA
基金
加拿大自然科学与工程研究理事会; 美国国家科学基金会;
关键词
OXIDATION; ALCOHOLS; BASICITY; HYDROXYPHTHALIMIDE; POTENTIALS; PROTON; SCALE; ACID;
D O I
10.1021/jacs.1c04181
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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.
引用
收藏
页码:10324 / 10332
页数:9
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