Kinetic deuterium isotope effects in the reactions of methyl iodide with azide and acetate ions in aqueous solution

1972 ◽  
Vol 76 (3) ◽  
pp. 427-432 ◽  
Author(s):  
Chong Min Won ◽  
Alfred V. Willi
Keyword(s):  
Aqueous Solution ◽  
Methyl Iodide ◽  
Isotope Effects ◽  
Deuterium Isotope Effects

A hydrogen-atom transfer mechanism in the oxidation of alcohols by [FeO4]2− in aqueous solution

2018 ◽  
Vol 47 (1) ◽  
pp. 240-245 ◽  
Author(s):  
Jianhui Xie ◽  
Po-Kam Lo ◽  
Chow-Shing Lam ◽  
Kai-Chung Lau ◽  
Tai-Chu Lau
Keyword(s):  
Aqueous Solution ◽  
Hydrogen Atom ◽  
Dft Calculations ◽  
Isotope Effects ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Bond Dissociation Energies ◽  
Dissociation Energies ◽  
Oxidation Of Alcohols ◽  
Deuterium Isotope Effects

The oxidation of alcohols by [FeO4]2− in aqueous solution is found to proceed via a hydrogen atom transfer (HAT) mechanism based on deuterium isotope effects, correlation between rate constants and bond dissociation energies (BDEs) and DFT calculations.

Kinetic deuterium isotope effects in the reaction of Vaska's compound (Ph3P)2Ir(CO)Cl with methyl iodide and MeOSO2CF3

1984 ◽  
Vol 3 (7) ◽  
pp. 1133-1134 ◽  
Author(s):  
Peter J. Stang ◽  
Melvyn D. Schiavelli ◽  
H. Keith Chenault ◽  
Julie L. Breidegam
Keyword(s):  
Methyl Iodide ◽  
Isotope Effects ◽  
Deuterium Isotope Effects

Kinetic deuterium isotope effect in the reaction of methyl iodide with thiosulfate ion in aqueous solution

1970 ◽  
Vol 48 (9) ◽  
pp. 1452-1455
Author(s):  
Alfred V. Willi ◽  
Chong Min Won
Keyword(s):  
Aqueous Solution ◽  
Gas Phase ◽  
Isotope Effect ◽  
Methyl Iodide ◽  
Isotope Effects ◽  
Force Constants ◽  
Deuterium Isotope Effect ◽  
Model Calculations ◽  
Bending Force ◽  
Reaction Vessels

The kinetic deuterium isotope effect in the reaction of methyl iodide with thiosulfate ion in aqueous solution has been determined as follows: kH/kD (per 3D) = 0.966 (+0.02°), 0.968 (+10.00°), 0.970 (+19.98°). Kinetic experiments have been carried out in reaction vessels with no gas phase. The experimental data are compared with results of model calculations of isotope effects from force constants. Excellent agreement between experimental and calculated isotope effects may be obtained with the following values of the transition state bending force constants: fHCI = 0.295 mdyn Å, fHCS = 0.300 to 0.320 mdyn Å. These values are equal to 50–65% of the corresponding bending force constants in stable molecules.

Kinetic deuterium isotope effects and kinetic solvent isotope effects for the solvolyses in water and in water + acetonitrile mixtures related to a series of substituted benzyl nitrates

1980 ◽  
Vol 58 (20) ◽  
pp. 2142-2145 ◽  
Author(s):  
Mohammed Ahsan ◽  
Ross Elmore Robertson ◽  
Michael Jesse Blandamer ◽  
John Marshall William Scott
Keyword(s):  
Aqueous Solution ◽  
Benzene Ring ◽  
Isotope Effect ◽  
Isotope Effects ◽  
Bond Breaking ◽  
Relative Importance ◽  
Stage Process ◽  
Deuterium Isotope Effects ◽  
Solvent Isotope ◽  
Solvent Isotope Effects

In aqueous solution, the α-deuterium isotope effects in the solvolyses of benzyl nitrates derivatives depend on the nature of the substituent in the benzene ring. In addition, the isotope effect for some derivatives depends on mole fraction of added acetonitrile while for others the isotope effect is insensitive to solvent composition. However, the kinetic solvent isotope effects for para-methyl and meta-trifluoromethyl derivatives remain unchanged when acetonitrile is added. These observations are accounted for in terms of a model which describes the solvolytic reaction as a two-stage process and contrasts the relative importance of bond-making and bond-breaking.

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