Kinetic Isotope Effects in the Reduction of Methyl Iodide

1999 ◽  
Vol 121 (3) ◽  
pp. 515-518 ◽  
Author(s):  
Torkil Holm
Keyword(s):  
Methyl Iodide ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope

13C kinetic isotope effects and reaction coordinate motions in transition states for SN2 displacement reactions

1976 ◽  
Vol 54 (7) ◽  
pp. 1146-1161 ◽  
Author(s):  
Warren Edward Buddenbaum ◽  
Vernon Jack Shiner Jr.
Keyword(s):  
Transition State ◽  
Isotope Effect ◽  
Methyl Iodide ◽  
Isotope Effects ◽  
Transition States ◽  
Kinetic Isotope Effects ◽  
Chloride Ions ◽  
Reaction Coordinate ◽  
Kinetic Isotope ◽  
State Models

Reaction coordinate motions and 13C kinetic isotope effects at 25 °C have been calculated for the SN2 reactions of methyl iodide with iodide, cyanide, and chloride ions and for the SN2 reaction of benzyl bromide with hydroxide ion using transition state models characterized by single interaction force constant, F12, between the bond being formed and the bond being broken. The isotope effect calculations show that the dependence of calculated 13C isotope effects on transition state symmetry found by Willi and Sims etal. holds true for reaction barriers corresponding to small values of νL, while the symmetry dependence observed by Bron holds true for barriers corresponding to large values of νL.νL was also found to have a strong influence on the reaction coordinate motions of the transition states. In particular, for the methyl iodide reactions an increase in νL increases the distortion of the methyl group in the direction expected for a classical SN2 reaction. Finally, reaction coordinate motions were used to show that the model proposed by Bron for the borderline region between SN1 and SN2 reaction mechanisms predicts an increase in the 13C kinetic isotope effect with decreasing total bond order and not the decrease suggested by Bron.

scholarly journals Inner Sphere and Outer Sphere Electron Transfer to Methyl Iodide. Deuterium and 13C Kinetic Isotope Effects.

1996 ◽  
Vol 50 ◽  
pp. 90-93 ◽  
Author(s):  
Torkil Holm ◽  
Ingolf Crossland ◽  
Hans Toftlund ◽  
Jon Songstad ◽  
Markku Leskelä ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Methyl Iodide ◽  
Isotope Effects ◽  
Outer Sphere ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope ◽  
Inner Sphere ◽  
Outer Sphere Electron Transfer

Primary and secondary kinetic isotope effects in proton (H+/D+) and chloronium ion (35Cl+/37Cl+) affinities

2001 ◽  
Vol 36 (10) ◽  
pp. 1140-1148 ◽  
Author(s):  
F�bio Cesar Gozzo ◽  
Marcos N. Eberlin
Keyword(s):  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope

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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