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Isomeric alkyl cation/arene complexes in the gas phase.
- Source :
-
Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2003 May 09; Vol. 9 (9), pp. 2072-8. - Publication Year :
- 2003
-
Abstract
- The kinetics and the stereochemistry of the protonation-induced unimolecular isomerization of (S)-(+)-1-D(1)-3-(p-tolyl)butane have been investigated in the gas phase in the 100-160 degrees C range. The process leads to the almost exclusive formation of the relevant meta isomer with complete racemization and partial 1,2-H shift in the migrating sec-butyl group. These results, together with the relevant activation parameters, point to the occurrence of low-energy, tightly bound isomeric sec-butyl cation/toluene complexes of defined structure and stability along the isomerization coordinate. The existence and the eta(1)-type structure of these low-energy intermediate species are confirmed by ab initio calculations on closely related systems at the MP2(full)/6-311++G**//HF/6-31+G** level of theory. Their role in the relevant energy surface clearly emerges from the comparison of the present results with those concerning sec-butylation of toluene carried out under comparable experimental conditions.
Details
- Language :
- English
- ISSN :
- 0947-6539
- Volume :
- 9
- Issue :
- 9
- Database :
- MEDLINE
- Journal :
- Chemistry (Weinheim an der Bergstrasse, Germany)
- Publication Type :
- Academic Journal
- Accession number :
- 12740856
- Full Text :
- https://doi.org/10.1002/chem.200204281