REACTION OF DIPHENYLCARBENE WITH METHANOL.

Article abstract of DOI:10.1021/ja00313a040

The reaction of triplet diphenylcarbene with methanol is believed to proceed via thermal excitation to the singlet state followed by reaction of that state with the alcohol. Analysis of the related reaction kinetics led to a reported enthalpy difference of 3-5 kcal mol** minus **1 between the singlet and its triplet ground state. The authors report measurements of the activation energy, E//o//b//s//d, for reaction of triplet diphenylcarbene with methanol in various solvents and find, for example, E//o//b//s//d equals 1. 66 plus or minus 0. 20 kcal mol** minus **1 in acetonitrile. These and other results are inconsistent with published interpretations of the data and dictate a reevaluation of earlier experiments and the mechanistic conclusions drawn from them.