Gas phase basicities of fluorocarbonyl compounds. An ion cyclotron resonance investigation of the effects of fluorine and trifluoromethyl substituents on hydroxy carbonium ion stabilities

Abstract

Gas phase proton affinities for a number of fluoro- and trifluoromethyl-substituted carbonyl compounds have been obtained using a combination of proton transfer equilibria and bracketing experiments. Absolute and relative substituent effects for F and CF3 on carbonyl basicities are determined and discussed in terms of inductive, resonance, polarization, and hydrogen bonding interactions. The data are used to interpolate basicities for HCOF and CF3CHO and are compared to theoretical ab initio calculations.