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Pnictogen Interaction Promotes Nitric Oxide (NO) Release via the NO2 Roaming Mechanism in 2-Nitropyridine
Prahlad Roy Chowdhury1, Sumitra Singh1, Monali Kawade1
1Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
None:
The role of the intramolecular N···N pnictogen interaction in the NO2 roaming mediated nitric oxide (NO) release in 2-nitropyridine is demonstrated. The dominance of the slow NO translational energy component over the corresponding fast component suggests that the NO2 roaming pathway for the NO release is favored in 2-nitropyridine, in contrast to nitrobenzene and 3-nitropyridine. The topography of a two-dimensional potential energy surface constructed using C-N (breaking) and C-O (forming) bonds as internal coordinates, in the T1 manifold, reveals that an intramolecular N···N pnictogen interaction between the nitrogen atom of the pyridine and the NO2 moiety in 2-nitropyridine favors the NO2 roaming pathway over the oxaziridine pathway.
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