Affiliation:
1. Department of Chemistry Zhejiang University 866 Yuhangtang Rd Hangzhou 310058 P. R. China
2. Center of Chemistry for Frontier Technologies ZJU-NHU United R&D Center Zhejiang University 866 Yuhangtang Rd Hangzhou 310058 P. R. China
3. State Key Laboratory of Chemical Engineering College of Chemical and Biological Engineering Zhejiang University 866 Yuhangtang Rd Hangzhou 310058 P. R. China
Abstract
AbstractThough electron transfer (ET) and proton transfer (PT) are extensively involved in organic reactions, they remain unclear in acid‐enabled disproportionation of nitroxyl radicals, especially in organic solvents. Here we unveil the acid‐promoted electron transfer (APET) mechanism with inverse kinetic isotope effect (KIE) for the disproportionation of 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) in CH3CN. Kinetic experiments relying on on‐line detection of electron paramagnetic resonance (EPR) was conducted together with theoretical calculations, giving consistent insights on the mechanisms. Moreover, the significant effect of water as cosolvent was revealed. The findings here will encourage further mechanistic understandings and method developments for nitroxyl‐participated organic reactions.
Funder
Zhejiang University
National Natural Science Foundation of China
Fundamental Research Funds for the Central Universities