Solvent Dependence of Enantioselectivity for a Base-Catalyzed 1,3-Hydron Transfer Reaction. A Kinetic Isotope Effect and NMR Spectroscopic Study

1995 ◽  
Vol 60 (5) ◽  
pp. 1356-1364 ◽  
Author(s):  
Marie Aune ◽  
Adolf Gogoll ◽  
Olle Matsson
Keyword(s):  
Spectroscopic Study ◽  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Transfer Reaction ◽  
Kinetic Isotope ◽  
Solvent Dependence

scholarly journals Kinetic Isotope Effect and Tunnelling in the Proton-transfer Reaction between 4-Nitrophenylnitromethane and Tetramethylguanidine in Toluene: A Reinvestigation.

1978 ◽  
Vol 32a ◽  
pp. 559-563 ◽  
Author(s):  
Otto Rogne ◽  
O. J. Kleppa ◽  
Nils Ingri ◽  
Elina Näsäkkälä ◽  
Otto Bastiansen ◽  
...  
Keyword(s):  
Proton Transfer ◽  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Transfer Reaction ◽  
Proton Transfer Reaction ◽  
Kinetic Isotope

Kinetic isotope effect and tunnelling in the proton transfer reaction between 2,4,6-trinitrotoluene and 1,1′,3,3′-tetramethylguanidine in dimethylformamide solvent

1979 ◽  
Vol 57 (6) ◽  
pp. 669-672 ◽  
Author(s):  
Arnold Jarczewski ◽  
Przemyslaw Pruszynski ◽  
Kenneth T. Leffek
Keyword(s):  
Proton Transfer ◽  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Transfer Reaction ◽  
Proton Transfer Reaction ◽  
Deuterium Isotope Effect ◽  
Kinetic Isotope ◽  
Enthalpy Of Activation ◽  
Entropy Of Activation ◽  
Large Primary

The proton transfer reaction between 2,4,6-trinitrotoluene and 1,1′,3,3′-tetramethylguanidine in dimethylformamide solvent shows a large primary deuterium isotope effect, kH/kD = 24.3 at 0 °C and 16.9 at 20 °C. The enthalpy of activation difference (ΔHD≠ − ΔHH≠) = 2.6 ± 0.4 kcal mol−1 and the entropy of activation difference (ΔSD≠ − ΔSH≠) = 3.4 ± 1.3 cal mol−1 K−1. This isotope effect, when fitted to Bell's equation, indicates that there is a considerable contribution to this reaction from tunnelling of the proton through the potential energy barrier.

Solvent Dependence of the Kinetic Isotope Effect in the Reaction of Ascorbate with the 2,2,6,6-Tetramethylpiperidine-1-oxyl Radical: Tunnelling in a Small Molecule Reaction

2010 ◽  
Vol 114 (10) ◽  
pp. 3423-3430 ◽  
Author(s):  
Ivana Sajenko ◽  
Viktor Pilepić ◽  
Cvijeta Jakobušić Brala ◽  
Stanko Uršić
Keyword(s):  
Isotope Effect ◽  
Small Molecule ◽  
Kinetic Isotope Effect ◽  
Molecule Reaction ◽  
Kinetic Isotope ◽  
Solvent Dependence

Direct dynamics calculation of the kinetic isotope effect for an organic hydrogen-transfer reaction, including corner-cutting tunneling in 21 dimensions

1993 ◽  
Vol 115 (17) ◽  
pp. 7806-7817 ◽  
Author(s):  
Yi Ping Liu ◽  
Da Hong Lu ◽  
Angels Gonzalez-Lafont ◽  
Donald G. Truhlar ◽  
Bruce C. Garrett
Keyword(s):  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Hydrogen Transfer ◽  
Transfer Reaction ◽  
Corner Cutting ◽  
Direct Dynamics ◽  
Hydrogen Transfer Reaction ◽  
Kinetic Isotope ◽  
Dynamics Calculation
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