A positive deviation of an α-nucleophile (a nucleophile bearing an unshared pair of electrons on an atom adjacent to the nucleophilic site) from a Brønsted-type plot of log k nuc vs. pKa constructed for a series of related normal nucleophiles. More generally, it is the influence of the atom bearing a lone pair of electrons on the reactivity at the adjacent site.
Note:
The use of the term has been extended to include the effect of any substituent on an adjacent reactive centre, for example in the case of the 'α-silicon effect'.
See also: Brønsted relation
Source:
PAC, 1994, 66, 1077. 'Glossary of terms used in physical organic chemistry (IUPAC Recommendations 1994)' on page 1088 (https://doi.org/10.1351/pac199466051077)