TY - JOUR
T1 - H/D exchange pathways
T2 - Flip-flop and relay processes
AU - Tian, Zhixin
AU - Reed, Dana R.
AU - Kass, Steven R.
PY - 2015/1/1
Y1 - 2015/1/1
N2 - Hydrogen-deuterium exchange reactions of 16 small rigid anions were examined using D2O, CH3OD, CH3CO2D, and (CF3)2C(CH3)OD. Bimolecular rate constants and extensive computations are reported. These deuterated reagents were used because D2O and CH3OD are weak acids that cannot react via sequential deuteron/proton transfers (i.e., the conventional H/D exchange mechanism of DePuy et al.) with the selected anions, and they provide a means to probe alternative pathways. The relative acidity of CH3CO2D and (CF3)2C(CH3)OD was measured (ΔΔHacid° = 1.1 ± 0.8 kcal mol-1) and their thermodynamic similarity but structural differences (i.e., the presence of a CO in the carboxylic acid but not the alcohol) were exploited to systematically investigate flip-flop and relay mechanisms. This has led to a number of generalizations relating to the occurrence of these pathways.
AB - Hydrogen-deuterium exchange reactions of 16 small rigid anions were examined using D2O, CH3OD, CH3CO2D, and (CF3)2C(CH3)OD. Bimolecular rate constants and extensive computations are reported. These deuterated reagents were used because D2O and CH3OD are weak acids that cannot react via sequential deuteron/proton transfers (i.e., the conventional H/D exchange mechanism of DePuy et al.) with the selected anions, and they provide a means to probe alternative pathways. The relative acidity of CH3CO2D and (CF3)2C(CH3)OD was measured (ΔΔHacid° = 1.1 ± 0.8 kcal mol-1) and their thermodynamic similarity but structural differences (i.e., the presence of a CO in the carboxylic acid but not the alcohol) were exploited to systematically investigate flip-flop and relay mechanisms. This has led to a number of generalizations relating to the occurrence of these pathways.
KW - 1 1 1 3 3 3-hexafluoro-2-methylpropanol
KW - Flip-flop and relay mechanisms
KW - Ftms
KW - Hydrogen-deuterium exchange
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U2 - 10.1016/j.ijms.2014.04.020
DO - 10.1016/j.ijms.2014.04.020
M3 - Article
AN - SCOPUS:85027925213
SN - 1387-3806
VL - 377
SP - 130
EP - 138
JO - International Journal of Mass Spectrometry
JF - International Journal of Mass Spectrometry
IS - 1
ER -