| Autor: |
Cartas-Rosado, R., Santoyo, M. E. Ruiz, Alvarez-Idaboy, J. R., Vivier-Bunge, A. |
| Zdroj: |
The Journal of Physical Chemistry - Part A; October 2001, Vol. 105 Issue: 40 p9222-9230, 9p |
| Abstrakt: |
In this work, the NO3 addition to alkenes has been studied using ab initio quantum chemistry methods. In addition to the commonly accepted NO3 radical addition to one of the C&dbd;C carbon atoms in alkenes, a symmetric transition state corresponding to the cycloaddition of the nitrate radical to the double bond has been identified, leading to the formation of a particularly stable NO3-alkene cyclic radical. Consideration of the cyclic adduct is necessary to explain the formation of carbonyl products derived from the cleavage of the C&dbd;C bond in the absence of oxygen. Yet, the possibility of its formation from the nitroalkyl open adduct radical R1R2C(ONO2)CR3R4· is hampered by the presence of a high energy barrier leading from the open to the cyclic adduct. The proposed cycloaddition channel is analogous to the Criegee mechanism for the cycloaddition of ozone to double bonds. |
| Databáze: |
Supplemental Index |
| Externí odkaz: |
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