Kinetic studies of outer-sphere redox reactions of .mu.-pyrazinedecaamminediruthenium (II,II), (II,III), and (III,III)

1986 ◽  
Vol 90 (16) ◽  
pp. 3686-3690 ◽  
Author(s):  
Urs Furholz ◽  
Albert Haim
Keyword(s):  
Redox Reactions ◽  
Kinetic Studies ◽  
Outer Sphere

Distinguishing between outer-sphere and inner-sphere redox mechanism on the basis of the solvent effect

1980 ◽  
Vol 45 (12) ◽  
pp. 3266-3269 ◽  
Author(s):  
Ľudovít Treindl ◽  
Ľubica Adamčíková
Keyword(s):  
Redox Reactions ◽  
Reaction Rate ◽  
Molar Fraction ◽  
Kinetic Studies ◽  
Outer Sphere ◽  
Diagnostic Value ◽  
Tert Butanol ◽  
Influence Of Water ◽  
Water Alcohol ◽  
Sphere Mechanism

During kinetic studies of redox reactions of U3+ ions, we paid special attention to the influence of water-alcohol binary mixtures on the reaction rate. Kinetic data suggest that the water-tert-butanol system is of a high diagnostic value. The dependence of log kexp on the molar fraction of tert-butanol passes through a characteristic minimum in the case of an outer-sphere mechanism, whereas in the other case it decreases monotonously.

Kinetics and mechanism of redox reactions of U(III) ions with monochloroacetic and dichloroacetic acids

1979 ◽  
Vol 44 (2) ◽  
pp. 401-405 ◽  
Author(s):  
Ľubica Adamčíková ◽  
Ľudovít Treindl
Keyword(s):  
Redox Reactions ◽  
Reaction Rate ◽  
Activation Parameters ◽  
Outer Sphere ◽  
Alcohol Concentration ◽  
Kinetics And Mechanism ◽  
Solvent Structure ◽  
Influence Of Ph ◽  
Sphere Mechanism

The kinetics and mechanism of the redox reactions of U3+ ions with mono- and dichloroacetic acids were studied. The influence of pH was observed mainly in the second case and led to the determination of the rate constants and activation parameters corresponding to two parallel steps, namely oxidation of U3+ with CHCl2COO- ions and oxidation of U3+ with CHCl2.COOH molecules. The influence of binary mixtures of water with methanol, ethanol, isopropanol, or tert-butenol on the reaction rate was followed. Increasing alcohol concentration influences the rate constant not only through changing dielectric constant and solvation of the reactants but also through a change of the solvent structure which plays a role in reactions with an outer sphere mechanism of the electron transfer.

scholarly journals Analyzing Mechanisms in Co(I) Redox Catalysis Using a Pattern Recognition Platform

2020 ◽  
Author(s):  
Tianhua Tang ◽  
Christopher Sandford ◽  
Shelley D. Minteer ◽  
Matthew Sigman
Keyword(s):  
Pattern Recognition ◽  
Bond Cleavage ◽  
Linear Regression Analysis ◽  
Benzyl Bromide ◽  
Kinetic Studies ◽  
Outer Sphere ◽  
Redox Catalysis ◽  
Tridentate Ligands ◽  
Electron Transfer Mechanism ◽  
Multivariable Linear Regression Analysis

Redox catalysis has been broadly utilized in electrochemical synthesis due to its kinetic advantages over direct electrolysis. The appropriate choice of redox mediator can avoid electrode passivation and overpotential, which strongly inhibit the efficient activation of substrates in electrolysis. Despite the benefits brought by redox catalysis, establishing the precise nature of substrate activation remains challenging. Herein, we determine that a Co(I) complex bearing two <i>N</i>,<i>N</i>,<i>N</i>-tridentate ligands acts as a competent redox catalyst for the reduction of benzyl bromide substrates. Kinetic studies combining electroanalytical techniques with multivariable linear-regression analysis were conducted, disclosing an outer-sphere electron-transfer mechanism, which occurs in concert with C–Br bond cleavage. Furthermore, we apply a pattern recognition platform to distinguish between mechanisms in the activation of benzyl bromides, found to be dependent on the ligation state of the cobalt(I) center and ligand used.

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