A compared study on the concerted reaction mechanism of cycloaddition between formaldehyde and ketene or ethylene

Abstract

The energy decomposition scheme has been used to study the concerted transition state (TS1 and TS2) for the titled reactions. DEF (deformation energy) and the interaction energy components ES (electrostatic energy), PL (polarization energy) and CT (charge transfer energy) for TS1 and TS2 are very similar, but EX (exchange repulsive energy) of TS1 is much smaller than TS2, thus leading to much higher activation barrier for reaction (2), H2C:CH2 + H2CO ?oxirane than reaction (1), H2C:C:O + H2CO ?2-oxooxirane. In order to decrease EX, the reaction (2) has to proceed in two-step (diradical) fashion.

Key words: REACTION MECHANISM, ETHYLENE, FORMALDEHYDE, CYCLOADDITION REACTION, KETENE, CONCERTED REACTION

CLC Number:

O621

Cite this article

FANG DECAI;FU XIAOYUAN. A compared study on the concerted reaction mechanism of cycloaddition between formaldehyde and ketene or ethylene[J]. Acta Chimica Sinica, 1994, 52(7): 658-662.

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