Subject: CCL: conformers and rate

From: Errol Lewars <elewars*at*trentu.cA>
Date: Thu, 08 Jul 2004 12:20:24 -0400

2004 July 8

The rate of formation of products Pa and Pb from quickly interconverting
conformers Ca and Cb is treated with the the Curtin/Hammett and
Winstein-Holness equations (the Curtin-Hammett principle, in particular,
is well-known): J. I Seeman, Chem Rev, 1983, 83, 83; E. L. Eliel, "From
Cologne to Chapel Hill", ACS, 1990, pp. 31-33.

Question: has anyone a reference to a discussion of the case of rapidly
interconverting conformers Ca and Cb, where Ca, although the minor
conformer, is the only one that can react with X to form a product CaX,
through transition state Ta; intuition aside, has someone explicitly
addressed whether the _experimental_ activation E is measuring the Ta-Ca
energy difference, or the Ta-Cb difference?

Thanks,

EL
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