Kinetics and mechanism of the oxidation of alcohols by tetrapropylammonium perruthenate

2005 ◽  
Vol 83 (9) ◽  
pp. 1212-1221 ◽  
Author(s):  
W David Chandler ◽  
Zhao Wang ◽  
Donald G Lee
Keyword(s):  
Reaction Mechanism ◽  
Isotope Effects ◽  
Second Order ◽  
Kinetics And Mechanism ◽  
Ruthenium Dioxide ◽  
Effective Catalyst ◽  
First Order ◽  
Oxidation Of Alcohols ◽  
Autocatalytic Process ◽  
Deuterium Isotope Effects

2-Propanol is oxidized by tetrapropylammonium perruthenate (TPAP) in a reaction that is second order in TPAP and first order in 2-propanol. One of the products, believed to be ruthenium dioxide, is an effective catalyst for the reaction, making it an autocatalytic process. The rate of oxidation is relatively insensitive to the presence of substituents. Primary kinetic deuterium isotope effects are observed when either the hydroxyl or the α hydrogen is replaced by deuterium. The only product obtained from the oxidation of cyclobutanol is cyclobutanone, indicating that the reaction is a two-electron process. Tetrahydrofuran is oxidized at a rate that is several orders of magnitude slower than that observed for 2-propanol, suggesting that the reaction of TPAP with alcohols may be initiated by formation of perruthenate esters. A tentative mechanism consistent with these observations is proposed.Key words: oxidation, alcohols, tetrapropylammonium perruthenate, reaction mechanism, autocatalysis.

scholarly journals Deuterium isotope effects in drug pharmacokinetics II: Substrate-dependence of the reaction mechanism influences outcome for cytochrome P450 cleared drugs

PLoS ONE ◽  
2018 ◽  
Vol 13 (11) ◽  
pp. e0206279 ◽  
Author(s):  
Hao Sun ◽  
David W. Piotrowski ◽  
Suvi T. M. Orr ◽  
Joseph S. Warmus ◽  
Angela C. Wolford ◽  
...  
Keyword(s):  
Cytochrome P450 ◽  
Reaction Mechanism ◽  
Isotope Effects ◽  
Substrate Dependence ◽  
Deuterium Isotope Effects ◽  
Drug Pharmacokinetics

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.

Kinetics and mechanism of disproportionation and ferricyanide oxidation of the 10-methylacridinium cation in aqueous base

1984 ◽  
Vol 62 (4) ◽  
pp. 729-735 ◽  
Author(s):  
John W. Bunting ◽  
Glenn M. Kauffman
Keyword(s):  
Ionic Strength ◽  
Second Order ◽  
Kinetics And Mechanism ◽  
Oxidation Pathway ◽  
First Order ◽  
Aqueous Base ◽  
Ph Range ◽  
Rate Profile ◽  
Kinetics Of ◽  
Major Oxidation

The kinetics of disproportionation and ferricyanide ion oxidation of the 10-methylacridinium cation have been measured spectrophotometrically over the pH range 9–14 in.20% CH3CN – 80% H2O (v/v) and ionic strength 1.0 at 25 °C. Disproportionation is kinetically second-order in total acridine species. The pH–rate profile is consistent with the rate-determining reaction of one acridinium cation with the pseudobase alkoxide anion derived from a second acridinium cation. Ferricyanide ion oxidation is kinetically first-order in each of ferricyanide ion and total acridine species. The pH–rate profile requires three distinct pathways for the ferricyanide ion oxidation of the 10-methylacridinium cation. For pH < 9.7, rate-determining attack of ferricyanide ion on the neutral pseudobase predominates, while for pH > 12.8 the predominant oxidation pathway involves reaction of ferricyanide ion with the pseudobase alkoxide ion. Between pH 9.7 and 12.8, the major oxidation pathway involves initial disproportionation of the acridinium cation followed by ferricyanide ion oxidation of the 9,10-dihydro-10-methylacridine product. This latter route accounts for a maximum of 69% of the total ferricyanide ion oxidation at pH 11.1.

Kinetics and mechanism of benzoylformate decarboxylase using carbon-13 and solvent deuterium isotope effects on benzoylformate and benzoylformate analogs

Biochemistry ◽  
1988 ◽  
Vol 27 (6) ◽  
pp. 2197-2205 ◽  
Author(s):  
Paul M. Weiss ◽  
George A. Garcia ◽  
George L. Kenyon ◽  
W. W. Cleland ◽  
Paul F. Cook
Keyword(s):  
Isotope Effects ◽  
Kinetics And Mechanism ◽  
Benzoylformate Decarboxylase ◽  
Deuterium Isotope Effects

Kinetics and Mechanism of Reaction of 2,4-Dinitrobenzaldehyde with Hydroxide Ion

1994 ◽  
Vol 59 (10) ◽  
pp. 2262-2268 ◽  
Author(s):  
Vladimír Macháček ◽  
Jana Manová ◽  
Miloš Sedlák ◽  
Vojeslav Štěrba
Keyword(s):  
Reaction Mechanism ◽  
Equilibrium Constant ◽  
Reaction Order ◽  
Kinetics And Mechanism ◽  
Hydroxide Ion ◽  
First Order ◽  
Mechanism Of Reaction

The reaction of 2,4-dinitrobenzaldehyde with hydroxide ion in water is first order in the substrate. The reaction order in hydroxide ion varies from one to two at lower and higher OH- concentrations, respectively. The reaction mechanism has been suggested, the pKa value of reaction product 2-nitro-4-nitrosophenol and the equilibrium constant of formation of the Meisenheimer adduct from 2-nitro-4-nitrosophenoxide and hydroxide ion have been determined.

The kinetics and mechanism of the reactions between carbon monoxide and ruthenium(II) chlorides in solution

1970 ◽  
Vol 48 (23) ◽  
pp. 3613-3618 ◽  
Author(s):  
B. C. Hui ◽  
B. R. James
Keyword(s):  
Carbon Monoxide ◽  
Molecular Nitrogen ◽  
Second Order ◽  
Kinetics And Mechanism ◽  
Gas Uptake ◽  
First Order ◽  
Kinetics Of Formation ◽  
Low Pressures ◽  
Kinetics Of ◽  
Hcl Solution

The kinetics of formation of mono- and dicarbonyl complexes in two successive stages by direct carbonylation of ruthenium(II) chlorides in dimethylacetamide solution have been studied at 65–80° and up to 1 atm CO by gas uptake techniques. Both stages are first order in ruthenium. Formation of the monocarbonyl is independent of CO pressure; dicarbonyl formation is first order in CO at low pressures with the order decreasing towards zero with increasing pressure, and shows an inverse chloride dependence from 0.1–2.0 M added chloride. For both stages, the data are consistent with a mechanism involving predissociation. A similar mechanism is suggested for the corresponding reactions in 3 M HCl solution which had been studied earlier and which showed overall second-order kinetics.Discussion on the related formation of molecular nitrogen complexes of ruthenium(II) is presented.

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