Back to Search
Start Over
A Substituent Effects Study Reveals the Kinetic Pathway for an interfacial Reaction.
- Source :
-
Journal of the American Chemical Society . 12/1/2004, Vol. 126 Issue 47, p15613-15617. 5p. - Publication Year :
- 2004
-
Abstract
- This paper describes the use of a substituent effects study to understand the mechanistic basis for an interfacial Diels -Alder reaction that does not proceed with standard second-order kinetics. Cyclopentadiene (Cp) undergoes a Diels-Alder reaction with a chemisorbed mercaptobenzoquinone to yield an immobilized Diels-Alder adduct. The pseudo-first-order rate constants are not linearly related to the concentration of diene, but they reach a limiting value with increasing concentrations of diene. The results of a substituent effects study support a mechanism wherein the electrochemical oxidation of hydroquinone produces two states of quinone. The first form, Q*, either reacts with Cp or isomerizes to 0, a form that is significantly less reactive with the diene. The interfacial reaction reaches a maximum rate when the concentration of diene is sufficiently high so that Q* undergoes complete Olels-Alder reaction and does not isomerize to Q. This work provides an example of the use of physical organic chemistry to understand an interfacial reaction. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00027863
- Volume :
- 126
- Issue :
- 47
- Database :
- Academic Search Index
- Journal :
- Journal of the American Chemical Society
- Publication Type :
- Academic Journal
- Accession number :
- 15429191
- Full Text :
- https://doi.org/10.1021/ja048978+