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Published on: February 24, 2015
Are pyridinium ylides radicals?
Fan Liao1, Wenhuan Huang1, Biao Chen1
1Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, China. zhxil@mail.ustc.edu.cn yiluo@ustc.edu.cn gzhang@ustc.edu.cn.
Abstract:
Pyridinium ylides are usually considered nucleophiles that can undergo various reactions involving electron pairs. However, it was found that ylides resulting from deprotonation of N-alkyl-substituted pyridinium salts exhibit radical characters, with no discernable NMR signals but decent EPR spectra in both solution and the solid state. An observed correlation between lowered π* energy level of the pyridinium ring and increased EPR activity indicates that thermally induced electron-transfer processes could be involved, where the variable-temperature EPR spectrum indicates a singlet ground state and a thermally activated triplet state for the ylide. The fact that the high-resolution mass spectrum confirms the presence of oligomers of a less sterically hindered pyridinium ylide further points to a radical mechanism.
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