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Theoretical study on the mechanism of the 1 CHCl + NO 2 reactions
Author(s) -
Zhang JiaXu,
Liu JingYao,
Li ZeSheng,
Sun ChiaChung
Publication year - 2004
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.20043
Subject(s) - chemistry , transition state , adduct , reaction mechanism , medicinal chemistry , reaction rate constant , molecule , bond cleavage , elementary reaction , product (mathematics) , computational chemistry , kinetics , catalysis , physics , organic chemistry , geometry , mathematics , quantum mechanics
The radical‐molecule reaction mechanism of 1 CHCl with NO 2 has been explored theoretically at the B3LYP/6‐311G( d, p ) and CCSD(T)/6‐311G( d, p ) (single‐point) levels of theory. Thirteen minimum isomers and 29 transition states are located. The initial association between 1 CHCl and NO 2 proceeds most likely through the carbon‐to‐middle‐nitrogen attack leading to an energy‐rich adduct a (HClCNO 2 ), which is found to be a barrierless process. Staring from a, the most feasible channel is to undergo a concerted O‐shift and CN bond rupture leading to product P 2 (NO + HClCO). The minor product pathways are the direct O‐extrusion of a to P 3 (O + HClCNO‐ cis ) as well as the 1,3‐H‐shift of a to isomer b (ClCNOOH) followed by a concerted OH‐shift leading to d (HOClCNO), which will dissociate to product P 8 (NO + ClCOH) via CN cleavage. Because the transition states and isomers involved in the most feasible channel all lie below the reactants, the title reaction is expected to be rapid, as is consistent with the measured rate constant at 296 K. The comparison with the analogous reactions 3 CH 2 + NO 2 are discussed. The present study may be useful for further experimental investigation of the title reaction. © 2004 Wiley Periodicals, Inc. J Comput Chem 25: 1184–1190, 2004