Photoelectron spectroscopy of anilinide and acidity of aniline

Abstract

The photoelectron spectrum of the anilinide ion has been measured. The spectrum exhibits a vibrational progression of the CCC in-plane bending mode of the anilino radical in its electronic ground state. The observed fundamental frequency is 524 ± 10 cm -1. The electron affinity (EA) of the radical is determined to be 1.607 ± 0.004 eV. The EA value is combined with the N-H bond dissociation energy of aniline in a negative ion thermochemical cycle to derive the deprotonation enthalpy of aniline at 0 K; δ acidH 0(PhHN-H) = 1535.4 ± 0.7 kJ mol -1. Temperature corrections are made to obtain the corresponding value at 298 K and the gas-phase acidity; δ acidH 298(PhHN-H) = 1540.8 ± 1.0 kJ mol -1 and δ acidG 298(PhHN-H) = 1509.2 ± 1.5 kJ mol -1, respectively. The compatibility of this value in the acidity scale that is currently available is examined by utilizing the acidity of acetaldehyde as a reference. © 2012 American Chemical Society.