Abstract
It is shown how the free energy profiles along and perpendicular to the reaction coordinate determine a two-dimensional energy surface for describing substituent effects in organic reactivity. This affords a generalization of the hyperbolic-paraboloid surfaces, extendible to large energy variations. It also shows that the reaction surface and curve-crossing approaches lead to a similar mathematical description of the problem. The various models are compared with experimental results for free energy of activation of proton-transfer reactions between benzoic acids and methanol and of Cope and Claisen rearrangements.
Original language | English |
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Pages (from-to) | 2192-2195 |
Number of pages | 4 |
Journal | Journal of Organic Chemistry |
Volume | 52 |
Issue number | 11 |
DOIs | |
State | Published - 1 May 1987 |