Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
5134406 | International Journal of Mass Spectrometry | 2017 | 5 Pages |
The equilibrium acidity of styrene was measured (ÎH°acid(PhCHCH2) = 390.6 ± 0.5 kcal molâ1) and its deprotonation site was revised from the ortho position on the aromatic ring to the α-hydrogen atom based upon deuterium-labeling studies and extensive computations. Somewhat surprisingly, the nature of the anionic base plays a critical role in properly determining the ionization site and avoiding misleading results due to extraordinary hydrogen-deuterium exchange. Bracketing the electron affinity of α-styryl radical (PhCCH2, 23.1 ± 3.4 kcal molâ1) enabled the α-CH bond dissociation energy (100.1 ± 3.4 kcal molâ1) of styrene and the effect of a phenyl substituent at an sp2-hybridized carbon to be determined. These results were compared to B3LYP, M06-2X, G3 and G4 computations.