Correlation of kinetic isotope effects with free energies of reaction

1980 ◽  
Vol 102 (26) ◽  
pp. 7797-7798 ◽  
Author(s):  
A. J. Kresge
Keyword(s):  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Free Energies ◽  
Kinetic Isotope

Some Kinetic and Equilibrium Isotope Effects in the Isobutylphenone Eno land Enolate Ion System

1989 ◽  
Vol 44 (5) ◽  
pp. 406-412 ◽  
Author(s):  
Y. Chiang ◽  
A. J. Kresge ◽  
P. A. Walsh
Keyword(s):  
Acetic Acid ◽  
Isotope Effect ◽  
Acid Catalysis ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Free Energies ◽  
Kinetic Isotope ◽  
Hydronium Ion ◽  
Acid Catalyzed ◽  
Water Catalysis

The following kinetic isotope effects were determined for acid-catalyzed ketonization of isobutyrophenone enol and enolate ion through rate-determining hydron transfer from catalyst to substrate: enol, kH/kD = 3.30±0.07 (hydronium ion catalysis), kH/kD = 4.0 + 2.8 (acetic acid catalysis); enolate ion, kH/kD= 1.00 + 0.21 (hydronium ion catalysis), kH/kD = 3A \ +0.20 (acetic acid catalysis), kH/kD = 7.48±0.23 (water catalysis). The magnitude of these isotope effects, when assessed in terms of the free energies of reaction for the processes in which they occur, are consistent with Melander-Westheimer- Bigeleisen theory. An equilibrium isotope effect of KH/KD = 5.88±0.32 was also determined for the ionization of isobutyrophenone enol as an oxygen acid.

Theoretical Simulations of Heavy-Atom Kinetic Isotope Effects in Aliphatic Claisen Rearrangement

2020 ◽  
Vol 124 (51) ◽  
pp. 10678-10686
Author(s):  
Yuqing Xu ◽  
Kin-Yiu Wong ◽  
Meishan Wang ◽  
Desheng Liu ◽  
Wenkai Zhao ◽  
...  
Keyword(s):  
Claisen Rearrangement ◽  
Isotope Effects ◽  
Heavy Atom ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope ◽  
Theoretical Simulations

Direct dynamics calculations of reaction rate and kinetic isotope effects in enzyme catalysed reactions

2002 ◽  
Vol 122 ◽  
pp. 223-242 ◽  
Author(s):  
Gary Tresadern ◽  
Sara Nunez ◽  
Paul F. Faulder ◽  
Hong Wang ◽  
Ian H. Hillier ◽  
...  
Keyword(s):  
Reaction Rate ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Direct Dynamics ◽  
Kinetic Isotope

Interpretation of Transient-State Kinetic Isotope Effects†

Biochemistry ◽  
1996 ◽  
Vol 35 (1) ◽  
pp. 83-88 ◽  
Author(s):  
Harvey F. Fisher ◽  
Swapan K. Saha
Keyword(s):  
Isotope Effects ◽  
Transient State ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope ◽  
State Kinetic
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