Ab initio molecular orbital calculations on dimethyl phosphate monoanion and dimethoxymethane demonstrate that antiperiplanar ester oxygen lone pairs significantly perturb the X-O (X = P or C) bond overlap populations. Specifically molecules in a gauche,trans conformation are "activated" for cleavage of the trans X-O bond. Other consequences of this torsional activation are discussed and presented in the context of a mechanism of action of ribonuclease A, staphylococcal nuclease, and lysozyme.
|Original language||English (US)|
|Number of pages||7|
|Journal||Journal of the American Chemical Society|
|State||Published - 1977|
ASJC Scopus subject areas