TY - JOUR
T1 - The isomerization of [H2O-C=O]o+ and [HC(=O)OH]o+ into [HO-C-OH]o+: proton-transport catalysis by CO
AU - Wong, C.Y.
AU - Ruttink, P.J.A.
AU - Burgers, P.C.
AU - Terlouw, J.K.
PY - 2004/5
Y1 - 2004/5
N2 - Mass spectrometry based experiments show that the m/z 46 ion generated in chemical ionization experiments of CO with a trace of water is not the previously proposed formic acid ion, HC(O)OH+ (1). Instead, the more stable dihydroxycarbene ion, HO–C–OH+ (2) is formed. A mechanistic analysis using the CBS-QB3 model chemistry supports the reaction sequence: (CO)2+ + H2O → H2O–CO+ (3), followed by the CO catalyzed isomerization: 3 + CO → 2 + CO. Solitary ions 1 and 2 do not interconvert, but theory and experiment agree that CO also efficiently catalyzes the conversion 1 → 2.
AB - Mass spectrometry based experiments show that the m/z 46 ion generated in chemical ionization experiments of CO with a trace of water is not the previously proposed formic acid ion, HC(O)OH+ (1). Instead, the more stable dihydroxycarbene ion, HO–C–OH+ (2) is formed. A mechanistic analysis using the CBS-QB3 model chemistry supports the reaction sequence: (CO)2+ + H2O → H2O–CO+ (3), followed by the CO catalyzed isomerization: 3 + CO → 2 + CO. Solitary ions 1 and 2 do not interconvert, but theory and experiment agree that CO also efficiently catalyzes the conversion 1 → 2.
U2 - 10.1016/j.cplett.2004.04.014
DO - 10.1016/j.cplett.2004.04.014
M3 - Article
SN - 0009-2614
VL - 390
SP - 176
EP - 180
JO - Chemical Physics Letters
JF - Chemical Physics Letters
IS - 1-3
ER -