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| - Ring Opening of the Cyclopropylcarbinyl Radical and Its N- andO-Substituted Analogues: A Theoretical Examination of Very FastUnimolecular Reactions
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| - High level ab initio molecular orbital calculations have been used to examine the ring opening ofthe cyclopropylcarbinyl radical and its heterosubstituted analogues. The applicability of various theoreticaltechniques to this ring-opening reaction has been investigated. A variant of the recently introduced CBS-RAD procedure is found to give good agreement with the experimental thermochemistry. The hybrid densityfunctional method B3-LYP is found to perform well for various geometry- and frequency-dependent quantitiesand to provide a possible economical alternative for the reliable prediction of the energetics. We find thatheterosubstitution by nitrogen at the 1-position has very little effect on the kinetics of ring opening. On theother hand, heterosubstitution by nitrogen or oxygen at the 2-position results in a significant rate enhancementfor an already rapid reaction. In both these latter cases, the kinetically preferred ring-opening pathway ispredicted not to lead to the thermodynamically preferred products.
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