Carbon Dioxide Stability and C═O π-Bond Strengths

Abstract

π-Bond energies for a series of C�O containing compounds including carbon dioxide are determined using G3 and W1 calculations. These two computational methods give results that are in good accord, and in the latter case span a 37 kcal mol −1 range from 75 (CH 2 �O) to 112 (CO 2 ) kcal mol −1 . This sensitivity to substituent effects on the π-bond strength is attributed to Coulombic interactions between the oppositely charged carbon and oxygen atoms in the carbon− oxygen double bond. In contrast, carbon−carbon π-bond energies of a related series of compounds are found to be relatively constant (i.e., the variation is only 3 kcal mol −1 ). The C�O π-bond strengths are also found to linearly correlate with the atomic charge at carbon as well as heats of hydration and hydrogenation.