Kinetics and mechanism of aquation and formation reactions of carbonato complexes. 12. Deuterium solvent isotope effect on the rate of acid-catalyzed decarboxylation of the carbonatobis(ethylenediamine)cobalt(III) complex ion. A mechanistic reappraisal

1978 ◽  
Vol 17 (7) ◽  
pp. 1892-1896 ◽  
Author(s):  
G. M. Harris ◽  
K. E. Hyde
Keyword(s):  
Isotope Effect ◽  
Kinetics And Mechanism ◽  
Solvent Isotope Effect ◽  
Acid Catalyzed ◽  
Solvent Isotope ◽  
Complex Ion

Solvent isotope effect in the acid-catalyzed isomerization of cis-stilbenes

1968 ◽  
Vol 33 (11) ◽  
pp. 4260-4261 ◽  
Author(s):  
Donald S. Noyce ◽  
Donald R. Hartter ◽  
Frank B. Miles
Keyword(s):  
Isotope Effect ◽  
Solvent Isotope Effect ◽  
Acid Catalyzed ◽  
Solvent Isotope

Kinetics and Mechanism for the Hydrolysis of Chlorothionoformate and Chlorodithioformate Esters in Water and Aqueous Acetone

1972 ◽  
Vol 50 (9) ◽  
pp. 1401-1406 ◽  
Author(s):  
D. M. McKinnon ◽  
A. Queen
Keyword(s):  
Isotope Effect ◽  
Structural Changes ◽  
Activation Parameters ◽  
Aqueous Acetone ◽  
Kinetics And Mechanism ◽  
Solvent Isotope Effect ◽  
Hydrocarbon Group ◽  
Solvent Isotope ◽  
Electron Donation ◽  
Hydrolysis Of

The effects of structural changes on the rates of hydrolysis of a series of chlorothionoformate esters and the analogous chlorodithioformate esters have been studied. For both classes of compound, the reactivity is enhanced by increased electron donation by the hydrocarbon group. These results, the activation parameters for the hydrolyses of the methyl compounds, and the solvent isotope effect are shown to be consistent with the operation of the SN1 mechanism.

Reactivity of Organophosphates. IV. Acid-catalyzed Hydrolysis of Triethyl Phosphate: a Comparison with Ethyl Acetate

1974 ◽  
Vol 52 (7) ◽  
pp. 1066-1071 ◽  
Author(s):  
Edward P. Lyznicki Jr. ◽  
Kiyotaka Oyama ◽  
Thomas T. Tidwell
Keyword(s):  
Ethyl Acetate ◽  
Isotope Effect ◽  
Bond Cleavage ◽  
Triethyl Phosphate ◽  
Solvent Isotope Effect ◽  
Mechanism Of Hydrolysis ◽  
Acid Catalyzed ◽  
Neutral Water ◽  
Solvent Isotope ◽  
Hydrolysis Of

The hydrolysis of triethyl phosphate in water and in 35% dioxane – 65% water has been examined. Hydrolysis in neutral water proceeds with a rate constant of 8.35 × 10−6 s−1 at 101°, ΔH* = 23.4 kcal/mol, ΔS* = −20 e.u., a solvent isotope effect [Formula: see text] of 1.3, C—O bond cleavage as shown by 18O labeling, and no catalysis by 0.5 M sulfuric acid. These results are consistent with the BAL2 mechanism of hydrolysis and the same pathway is indicated for the reaction in neutral 35% dioxane –65% water. Perchloric acid catalyzes the reaction in dioxane–water with C—O bond cleavage in 0.904 M acid, ΔH* = 24.1 kcal/mol, ΔS* = −17 e.u., and the solvent isotope effect [Formula: see text] in 0.556 M acid. These results indicate that the AAL2 pathway of hydrolysis is followed under these conditions. The reactivity of triethyl phosphate is compared with that of ethyl acetate.

Kinetic solvent isotope effect on acid-catalyzed hydrolysis of hydroxamic acids

1991 ◽  
Vol 45 (1) ◽  
pp. 79-84 ◽  
Author(s):  
Kallos K. Ghosh ◽  
Shiv G. Tandon
Keyword(s):  
Isotope Effect ◽  
Hydroxamic Acids ◽  
Solvent Isotope Effect ◽  
Acid Catalyzed ◽  
Solvent Isotope ◽  
Hydrolysis Of

Kinetic solvent isotope effect studies on the methanolysis of 1-phenylethyl chlorides

1993 ◽  
Vol 6 (6) ◽  
pp. 361-366 ◽  
Author(s):  
Ikchoon Lee ◽  
Won Heui Lee ◽  
Hai Whang Lee
Keyword(s):  
Isotope Effect ◽  
Solvent Isotope Effect ◽  
Solvent Isotope

Neutral Solvolysis of Acyl Carbon and the Temperature Dependence of the Kinetic Solvent Isotope Effect

1975 ◽  
Vol 53 (6) ◽  
pp. 869-877 ◽  
Author(s):  
B. Rossall ◽  
R. E. Robertson
Keyword(s):  
Temperature Dependence ◽  
Isotope Effect ◽  
Solvent Isotope Effect ◽  
Acyl Carbon ◽  
Rate Of Hydrolysis ◽  
Solvent Isotope ◽  
Neutral Conditions ◽  
Hydrolysis Of

The temperature dependence of the rate of hydrolysis of benzoic, phthalic, and succinic anhydrides have been determined in H2O and D2O under "neutral" conditions. Corresponding data have been obtained for methyl trifluoroacetate. While both series supposedly react by the same BAc2 mechanism, remarkable differences are made obvious by this investigation. Possible sources of such differences are proposed.

Proton-coupled electron transfer between [Ru(bpy)2(py)OH2]2+ and [Ru(bpy)2(py)O]2+. A solvent isotope effect (kH2O/kD2O) of 16.1

1981 ◽  
Vol 103 (10) ◽  
pp. 2897-2899 ◽  
Author(s):  
Robert A. Binstead ◽  
Bruce A. Moyer ◽  
George J. Samuels ◽  
Thomas J. Meyer
Keyword(s):  
Electron Transfer ◽  
Isotope Effect ◽  
Solvent Isotope Effect ◽  
Proton Coupled Electron Transfer ◽  
Solvent Isotope

An Unusual Solvent Isotope Effect in the Reaction of W(CO)5(solv) (solv = Cyclohexane or Cyclohexane-d12) with THF

2000 ◽  
Vol 19 (9) ◽  
pp. 1682-1691 ◽  
Author(s):  
Riki Paur-Afshari ◽  
J. Lin ◽  
Richard H. Schultz
Keyword(s):  
Isotope Effect ◽  
Solvent Isotope Effect ◽  
Solvent Isotope

Notizen: 67Zn NMR Anomalous Solvent Isotope Effect in Aqueous Solutions

1974 ◽  
Vol 29 (4) ◽  
pp. 660-661 ◽  
Author(s):  
B. W. Epperlein ◽  
H. Krüger ◽  
. Lutz ◽  
A. Schwenk
Keyword(s):  
Aqueous Solutions ◽  
Isotope Effect ◽  
Solvent Isotope Effect ◽  
Zinc Bromide ◽  
The Difference ◽  
Solvent Isotope

For 67Zn NMR lines of solutions of ZnCl2, ZnBr2, and ZnI2 in H2O and D2O an anomalous solvent isotope effect is reported. In D2O solutions the lines are shifted to higher frequencies. The difference between the shieldings in H2O and D2O is e.g. σ(H2O) - σ(D2O) = (13.1 ±0.7) ppm for a concentration of 0.02 moles zinc bromide per mole solvent.

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