Reactivity and Secondary Kinetic Isotope Effects in the SN2 Reaction Mechanism:  Dioxygen Radical Anion and Related Nucleophiles

2000 ◽  
Vol 122 (8) ◽  
pp. 1740-1748 ◽  
Author(s):  
Gustavo E. Davico ◽  
Veronica M. Bierbaum
Keyword(s):  
Reaction Mechanism ◽  
Radical Anion ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope ◽  
Sn2 Reaction

Reactions of Muonium with simple biochemical solutes in water and micelles

1991 ◽  
Vol 69 (8) ◽  
pp. 1252-1258 ◽  
Author(s):  
Mary V. Barnabas ◽  
David C. Walker
Keyword(s):  
Reaction Mechanism ◽  
Organic Compounds ◽  
Rate Constants ◽  
Enhancement Factor ◽  
Isotope Effects ◽  
Ph Dependence ◽  
Kinetic Isotope Effects ◽  
Natural State ◽  
Sugar Phosphate ◽  
Kinetic Isotope

Rate constants are reported for the reaction of muonium atoms in water with some 36 organic compounds, many of interest in biology. These kM values range from < l05 to 7 × 1010 M−1 s−1, according to the type of reaction involved, with the sugar–phosphate backbones of nucleic acids being at the low end and their bases at the high end. They are compared with corresponding published H-atom data (kH), where possible, and show kinetic-isotope-effects ranging over five orders of magnitude. Since all kH data were obtained at pH = 1, while kM values refer to pH ~ 7 of the natural state, the pH-dependence of kM was examined in representative cases. The changes found result from protonation of the solute rather than a changed reactivity of Mu on being converted to MuH+. On localizing the solutes in the hydrophobic phase of dilute micelles, the reactivity of Mu was again measured (kM(mic)). The resulting "enhancement" factor was considered in terms of: the reaction mechanism, its dependence on microenvironment (solvation), and the concentrating effect of mutual confinement to small sections of a biphasal system. Key words: kinetic isotope effects, muonium, biochemicals, micelles.

The Effect of Solvent on the Structure of the Transition State for the SN2 Reaction between Cyanide Ion and Ethyl Chloride in DMSO and THF Probed with Six Different Kinetic Isotope Effects

2006 ◽  
Vol 71 (13) ◽  
pp. 4742-4747 ◽  
Author(s):  
Yao-ren Fang ◽  
Susanna MacMillar ◽  
Jonas Eriksson ◽  
Magdalena Kołodziejska-Huben ◽  
Agnieszka Dybała-Defratyka ◽  
...  
Keyword(s):  
Transition State ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Ethyl Chloride ◽  
Cyanide Ion ◽  
Effect Of Solvent ◽  
Kinetic Isotope ◽  
Sn2 Reaction

scholarly journals Ensemble-Averaged QM/MM Kinetic Isotope Effects for the SN2 Reaction of Cyanide Anions with Chloroethane in DMSO Solution

2012 ◽  
Vol 18 (30) ◽  
pp. 9405-9414 ◽  
Author(s):  
J. Javier Ruiz Pernía ◽  
Ian H. Williams
Keyword(s):  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Dmso Solution ◽  
Kinetic Isotope ◽  
Sn2 Reaction

scholarly journals Enzymatic Δ1-Dehydrogenation of 3-Ketosteroids—Reconciliation of Kinetic Isotope Effects with the Reaction Mechanism

ACS Catalysis ◽  
2021 ◽  
pp. 8211-8225
Author(s):  
Michał Glanowski ◽  
Patrycja Wójcik ◽  
Magdalena Procner ◽  
Tomasz Borowski ◽  
Dawid Lupa ◽  
...  
Keyword(s):  
Reaction Mechanism ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Kinetic Isotope
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