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Theoretical study on reaction mechanism of the fluoromethylene radical with nitrogen dioxide

✍ Scribed by Jia-Xu Zhang; Jing-Yao Liu; Ze-Sheng Li; Chia-Chung Sun

Publisher
John Wiley and Sons
Year
2004
Tongue
English
Weight
308 KB
Volume
25
Category
Article
ISSN
0192-8651

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✦ Synopsis

Abstract

The complex doublet potential energy surface for the reaction of ^1^CHF with NO~2~, including 14 minimum isomers and 30 transition states, is explored theoretically at the B3LYP/6‐311G(d,p) and CCSD(T)/6‐311G(d,p) (single‐point) levels of theory. The initial association between ^1^CHF and NO~2~ is found to be the carbon‐to‐middle‐nitrogen attack forming an energy‐rich adduct a (HFCNO~2~) with no barrier, followed by concerted O‐shift and CN bond rupture leading to product P~2~ (NO + HFCO), which is the most abundant. In addition, a can take a 1,3‐H‐shift to isomer b (FCN(O)OH) followed by the dissociation to form the second feasible product P~4~ (OH + FCNO). The least favorable pathway is that b undergoes a concerted OH‐shift to form d (HO(F)CNO), which will dissociate to product P~5~ (HF+OCNO) via side HF‐elimination. The secondary dissociation of P~5~ may form product P~7~ (HF+NO+CO) easily. Furthermore, the ^1^CHF attack at the end‐O of NO~2~ is a barrier‐consumed process, and thus may only be of significance at high temperatures. The comparison with the analogous reactions ^1^CHCl + NO~2~ is discussed. The present study may be helpful for probing the mechanism of the title reaction and understanding the halogenated carbine chemistry. © 2004 Wiley Periodicals, Inc. J Comput Chem 25: 1888–1894, 2004

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