Electrostatic potential as a measure of gas phase carbocation stability
2006 (English)In: International Journal of Quantum Chemistry, ISSN 0020-7608, E-ISSN 1097-461X, Vol. 106, no 14, 2904-2909 p.Article in journal (Refereed) Published
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.
Place, publisher, year, edition, pages
2006. Vol. 106, no 14, 2904-2909 p.
carbocations, carbenium ions, relative stabilities, electrostatic potentials, atoms, ion, trinitromethanide, stabilization, heterolysis, molecules, cations, salts, c3h3+, bond
IdentifiersURN: urn:nbn:se:kth:diva-16065DOI: 10.1002/qua.21115ISI: 000241276800011ScopusID: 2-s2.0-33750897170OAI: oai:DiVA.org:kth-16065DiVA: diva2:334107
QC 20100525. Conference: 5th Congress of the International-Society-for-Theoretical-Chemical-Physics. New Orleans, LA. JUL 20-26, 20052010-08-052010-08-052016-06-01Bibliographically approved