TY - JOUR
T1 - Hydrogen atom or proton transfer in neutral and single positive ions of salicylic acid and related compounds
AU - Rodríguez-Santiago, L.
AU - Sodupe, M.
AU - Oliva, A.
AU - Bertran, J.
PY - 1999/9/29
Y1 - 1999/9/29
N2 - The nature of the process 'hydrogen atom' or 'proton' transfer reaction in neutral and single positive ions of salicylic acid, o-hydroxybenzaldehyde, and salicylaldimine has been studied using the B3LYP density functional method. Single-point calculations at the CCSD(T) level have also been performed. For neutral systems, the reaction corresponds to a proton transfer process coupled with an important electronic transfer, which leads to a compound with nonzwitterionic character. A similar behavior is observed for ionized π radical cations. In ionized σ states, however, the process is that of a hydrogen transfer. In all cases, π ionization strengthens the initial H-bond and favors the reaction. For some of the systems the proton transfer occurs spontaneously.
AB - The nature of the process 'hydrogen atom' or 'proton' transfer reaction in neutral and single positive ions of salicylic acid, o-hydroxybenzaldehyde, and salicylaldimine has been studied using the B3LYP density functional method. Single-point calculations at the CCSD(T) level have also been performed. For neutral systems, the reaction corresponds to a proton transfer process coupled with an important electronic transfer, which leads to a compound with nonzwitterionic character. A similar behavior is observed for ionized π radical cations. In ionized σ states, however, the process is that of a hydrogen transfer. In all cases, π ionization strengthens the initial H-bond and favors the reaction. For some of the systems the proton transfer occurs spontaneously.
U2 - 10.1021/ja990919m
DO - 10.1021/ja990919m
M3 - Article
VL - 121
SP - 8882
EP - 8890
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 38
ER -