Decarbonylation of the 2-Hydroxypyridine Radical Cation: A Computational Study

作者：Choe Joong Chul^*

来源：Bulletin of the Korean Chemical Society, 2014, 35(10): 3021-3024.

DOI：10.5012/bkcs.2014.35.10.3021

• 2-Pyridone ion
• Potential energy surface
• G3 calculation
• RRKM calculation
• Kinetics

The potential energy surface (PES) for the dissociation of the 2-hydroxypyridine (2-HP) radical cation was determined from G3//B3LYP calculations, including the loss of CO, HCN, and HNC. The formation of the 1H-pyrrole radical cation by decarbonylation through a more stable tautomer, the 2-pyridone (2-PY) radical cation, was the most favorable dissociation pathway. Kinetic analysis by the Rice-Ramsperger-Kassel-Marcus model calculations was carried out based on the obtained PES. It is proposed that the dissociation occurs after a rapid tautomerization to 2-PY center dot+, and that most of the ions generated by ionization of 2-HP have the structure of 2-PY center dot+ at equilibrium above the tautomerization barrier.

• 出版日期2014-10-20