Henry Rzepa's Blog Chemistry with a twist

January 13, 2019

Free energy relationships and their linearity: a test example.

Linear free energy relationships (LFER) are associated with the dawn of physical organic chemistry in the late 1930s and its objectives in understanding chemical reactivity as measured by reaction rates and equilibria.

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May 29, 2011

The inner secrets of an ion-pair: Isobornyl chloride rearrangements.

Observation of the slow racemization of isobornyl chloride in a polar solvent in 1923-24 by Meerwein led to the recognition that mechanistic interpretation is the key to understanding chemical reactivity. The hypothesis of ion pairs in which a chloride anion is partnered by a carbocation long ago entered the standard textbooks (see DOI 10.1021/ed800058c and 10.1021/jo100920e for background reading). But the intimate secrets of such ion-pairs are still perhaps not fully recognised. Here, to tease some of them them out, I use the NCI method, which has been the subject of several recent posts.

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