Abstract
The energetics of the ring-expanding rearrangement of the 1-oxaspiro[4.5]deca-6,9-dien-8-ylium ion 14 involving a 1,2-shift of either carbon or oxygen have been investigated through molecular orbital calculations at the semiempirical (AM1), ab initio (HF/z, HF/6-31G* and MP2/6-31G*) and density functional (B3LYP/6-31G*) levels of approximation. Our results have shown that rearrangement via migration by carbon is thermodynamically (and probably also kinetically) favoured over the alternative 1,2-shift by oxygen. The geometries and charge distributions computed for the structure 14 as well as the rearranged cations and possible transition structures are also described.
Original language | English |
---|---|
Pages (from-to) | 204-208 |
Number of pages | 5 |
Journal | Journal of the Chemical Society: Perkin Transactions 2 |
Issue number | 2 |
DOIs | |
Publication status | Published - 2002 |