Title of article
Ab initio and density functional study of the 5-pentacyclo[6.2.1.13,6.02,7.04,10]dodecyl cation. A symmetrical μ-hydride bridged carbocation
Author/Authors
Carneiro، نويسنده , , José Walkimar de M. and Taft، نويسنده , , Carlton A. and de Paula e Silva، نويسنده , , Carlos H.T. and Tostes، نويسنده , , José Glauco R. and Seidl، نويسنده , , Peter R. and Pinto، نويسنده , , Paulo Sérgio da S. and Costa، نويسنده , , Valentim Em??lio U. and Alifantes، نويسنده , , Jo?o، نويسنده ,
Issue Information
روزنامه با شماره پیاپی سال 2001
Pages
6
From page
189
To page
194
Abstract
MP2/6-31g(d,p) and B3LYP/6-31g(d,p) calculations for the pentacyclo[6.2.1.13,6.02,7.04,10]dodecyl cation reveal two minima on the potential energy surface. The most stable minimum is the μ-hydride bridged cation 2. The second minimum is the two-electron three-center bonded structure 3. At MP2/6-31g(d,p) 2 is only 0.2 kcal/mol more stable than 3, but at B3LYP/6-31g(d,p) this energy difference increases to 3.3 kcal/mol. The energy difference between 2 and 3 is only 3.8 kcal/mol. Solvent effect does not affect these numbers significantly. This low energy barrier may account for the product distribution observed on solvolysis of pentacyclic derivatives.
Journal title
Chemical Physics Letters
Serial Year
2001
Journal title
Chemical Physics Letters
Record number
1777545
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