H/D exchange pathways: Flip-flop and relay processes

Zhixin Tian; Dana R. Reed; Steven R. Kass

doi:10.1016/j.ijms.2014.04.020

H/D exchange pathways: Flip-flop and relay processes

Zhixin Tian, Dana R. Reed, Steven R. Kass

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

5 Scopus citations

Abstract

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 (ΔΔH_acid° = 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.

Original language	English (US)
Pages (from-to)	130-138
Number of pages	9
Journal	International Journal of Mass Spectrometry
Volume	377
Issue number	1
DOIs	https://doi.org/10.1016/j.ijms.2014.04.020
State	Published - 2015

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© 2014 Elsevier B.V. All rights reserved.

Keywords

1 1 1 3 3 3-hexafluoro-2-methylpropanol
Flip-flop and relay mechanisms
Ftms
Hydrogen-deuterium exchange

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title = "H/D exchange pathways: Flip-flop and relay processes",

abstract = "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.",

keywords = "1 1 1 3 3 3-hexafluoro-2-methylpropanol, Flip-flop and relay mechanisms, Ftms, Hydrogen-deuterium exchange",

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T2 - Flip-flop and relay processes

AU - Tian, Zhixin

AU - Reed, Dana R.

AU - Kass, Steven R.

PY - 2015

Y1 - 2015

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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ER -

H/D exchange pathways: Flip-flop and relay processes

Abstract

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Keywords

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