Proton affinity and heat of formation of vinyloxy [CH2CHO]* and Acetonyl [CH2COCH3]* radicals.

Abstract : Frequently found in hydrocarbon oxidation and in the photochemistry of carbonyl compounds, the β-carbonyl radicals are of interest. The experimental proton affinities of the two title radicals have been determined from proton transfer reactions (as shown) monitored in an FT-ICR mass spectrometer. This led to an estimation of their heats of formation (1: 13±3; 2: -34±3 kJ mol(-1)). Ab initio molecular orbital calculations, up to the G2 level, confirmed these results.