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- Robbins, Adele M., et al.
(författare)
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Electrostatic potential as a measure of gas phase carbocation stability
- 2006
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Ingår i: International Journal of Quantum Chemistry. - : Wiley. - 0020-7608 .- 1097-461X. ; 106:14, s. 2904-2909
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Tidskriftsartikel (refereegranskat)abstract
- Assessment of the relative stabilities of carbocations is important for interpreting reaction mechanisms as well as in organic synthesis. A common approach is in terms of hydride affinities; however these depend on a second system, a neutral molecule, as well as the ion. In the present work, we propose a measure of gas phase carbocation stability that is dependent solely on the properties of the ion: the magnitude of the most positive surface electrostatic potential associated with the carbon framework. This quantity, labeled V-S,V-max, reflects a key factor, the extent to which the positive charge has been delocalized. We have computed V-S,V-max for 28 carbocations, and we show that the overall trends predicted are physically meaningful in terms of experimental observations. Mulliken atomic charges are not satisfactory for this purpose.
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