置換反応における質量効果

概要

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In dealing with substituent effects in chemical reactions, only two factors are usually taken into account. They are the polar effect pertaining to charge distribution and the steric effect pertaining to bulk distribution. One more factor must be considered, that is, the ponderal effect pertaining to mass distribution within the molecule under consideration. The ponderal effect is discussed in detail for the Finkelstein exchange, Y-+RX→YR+X- (X, Y=isotopically or chemically different halogens ; R=Me, Et, n-Pr, i-Pr, t-Bu, i-Bu, neoPe), and in brief for a few more reactions. Nonpotential energy effects, including ponderal, may be of particular importance in both surface and enzymatic catalyses. In these catalyses the substrate adsorbs on the catalyst surface or coordinates to the enzyme, resulting in the loss of translational and rotational freedoms. This loss may give rise to quite a large ponderal entropy effect.
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