Stereoelectronic Properties of Tetrahedral Species derived from Carbonyl Groups. Ab initio study of the hydroxymethanes

Analysis of the electronic structure of the hydroxymethanes provides a consistent picture of stereoelectronic effects in such molecules: The average CO bond length decreases in the series methanol, methanediol, methanetriol. An oxygen (O′) lone pair, which is trans‐anti‐periplanar (app) to another oxygen (O″), shortens and strengthens the CO′ bond and simultaneously lengthens and weakens the CO′ bond. This is consistent with solid state structural evidence and with the reactivity patterns of tetrahedral species resulting from nucleophilic addition to a carbonyl group.