A b i n i t i o molecular orbital calculations on the reaction path of the ketocarbene–ketene rearrangement

Abstract

An ab initio type SCF MO study using a double zeta quality basis set has been carried out on the formylmethylene–ketene rearrangement reaction which is the last step of the Wolff rearrangement–decomposition sequence of α‐diazoketones and α‐diazoesters. The ketene structure is computed to be 74.3 kcal/mole more stable than the isomeric formylmethylene and the reaction features a computed activation energy of 5.7 kcal/mole, corresponding to a bridged activated complex. The computed geometry of the ketene molecule is in good agreement with the experimental geometry.