Showing papers by "Eamonn F. Healy published in 1987"
TL;DR: In this article, the chair Cope rearrangement of 1,5-hexadiene was investigated up to MP4SDQ/6-31 G* level and it was shown that the reaction takes place via a biradicaloid intermediate.
49 citations
45 citations
TL;DR: The magnitudes of secondary deuterium isotope effects (SDIE) are generally in the range of 0.9 − 1.25 as mentioned in this paper, and are often satisfactorily rationalized by the zero point energy (ZPE) change on going from reactant to transition state due to C-H rehybridization.
Abstract: The magnitudes of secondary deuterium isotope effects (SDIE) are generally in the range of 0.9 < k/sub H//k/sub D/ < 1.25, and are often satisfactorily rationalized by the zero-point energy (ZPE) change on going from reactant to transition state due to C-H rehybridization. They now report a far larger SDIE for the title reaction. Its rationalization on the basis of transition state theory suggests that it more closely resembles a primary isotope effect.
22 citations
TL;DR: In this article, the MP4SDO/6-31G* level for corner-protonated cyclopropane has been shown to have an unsymmetrical π complex structure, the formal charges on the basal atoms being in the ratio 3:2; implications concerning the norbornyl cation are discussed.
Abstract: Calculations have been carried out at the MP4SDO//6-31G* level for corner-protonated cyclopropane that show it to have an unsymmetrical π complex structure, the formal charges on the basal atoms being in the ratio 3:2; implications concerning the norbornyl cation are discussed.
15 citations