Abstract
The mechanisms of CH2I with NO2 reaction were investigated on the singlet and triplet potential energy surfaces (PESs) by the UB3LYP method. The energetic information is further refined at the UCCSD(T) and UQCISD(T) levels of theory. Our results indicated that the title reaction is more favorable on the singlet PES thermodynamically, and less competitive on the triplet one. On the singlet PES, the title reaction is most likely to be initiated by the carbon-to-oxygen approach forming the adduct IM1 (H2ICONO-trans) without any transition state, which can isomerizes to IM2 (H2ICNO2) and IM3 (H2ICONO-cis), respectively. The most feasible pathway is the 1, 3-I shift with C–I and O–N bonds cleavage along with the N–I bond formation of IM1 lead to the product P1 (CH2O + INO), which can further dissociate to give P3 (CH2O + I + NO). The competitive pathway is 1, 3-H shift associated with O–N bond rupture of IM1 to form P2 (CHIO + HNO). The theoretically obtained major product CH2O and adducts IM1 and IM2 are in good agreement with the kinetic detection in experiment. The similarities and discrepancies between CH2I + NO2 and CH2Br + NO2 reactions are discussed in terms of the electronegativity of halogen atom and the barrier height of the rate-determining process. The present study may be helpful for further experimental investigation of the title reaction.
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