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The Naphthylcarbene Potential Energy Hypersurface
- Source :
- Journal of the American Chemical Society. 119:1370-1377
- Publication Year :
- 1997
- Publisher :
- American Chemical Society (ACS), 1997.
-
Abstract
- The naphthylcarbene potential energy surface (PES) was examined ab initio, employing self-consistent field (SCF), second-order perturbation theory (MP2), and density functional (Becke3LYP) methods in conjunction with 6-31G*, DZ, DZP, and 6-311+G* basis sets. All stationary structures were characterized by vibrational frequency analyses at the Becke3LYP/6-31G* level; final energies were evaluated at the Becke3LYP/6-311+G*//Becke3LYP/6-31G* + ZPVE level. Cyclobuta[de]naphthalene is the global minimum on this part of the C11H8 PES. Generally, seven-membered benzocarbenes are no minima as they converge to their corresponding allenes. Both 1- and 2-naphthylcarbene have triplet ground states, but the small S−T gaps (ca. 5 kcal mol-1) allow facile rearrangements in the singlet manifold to take place. The triplet rotational barrier for the exo-methylene in 2-naphthylcarbene is relatively small (3.5 kcal mol-1) due to weak π-bonding. At low temperatures, singlet 2-naphthylcarbene equilibrates with 2,3-benzobicyclo...
Details
- ISSN :
- 15205126 and 00027863
- Volume :
- 119
- Database :
- OpenAIRE
- Journal :
- Journal of the American Chemical Society
- Accession number :
- edsair.doi...........71d728f64a8a810b21d18ed294d21261