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J Am Chem Soc. 2001 Mar 14;123(10):2377-87.

Electron-transfer-induced tautomerization in methylindanones: electronic control of the tunneling rate for enolization.

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  • 1Contribution from the Institute of Physical Chemistry, University of Fribourg, Perolles, CH-1700 Fribourg, Switzerland.


The radical cations generated from 4-methyl- and 4,7-dimethylindanone, as well as their deuterated isotopomers, isolated in Argon matrices, were found to undergo enolization to the corresponding enol radical cations at rates that differ by orders of magnitude. It is shown by quantum chemical calculations that the effect of the remote methyl group in the 4-position is of purely electronic nature in that it stabilizes the unreactive pi-radical relative to the reactive sigma-radical state of the 7-methylindanone radical cation. The observed kinetic behavior of the two compounds can be reproduced satisfactorily on the basis of calculated height and width of the thermal barrier for enolization, using the Bell model for quantum mechanical tunneling. High-level calculations on the methylacrolein radical cation show that barriers for enolization in radical cations are overestimated by B3LYP/6-31G.

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