Variable-Temperature Microelectrode Voltammetry:  Application to Diffusion Coefficients and Electrode Reaction Mechanisms

1999 ◽  
Vol 103 (15) ◽  
pp. 2963-2969 ◽  
Author(s):  
Sarah R. Jacob ◽  
Qi Hong ◽  
Barry A. Coles ◽  
Richard G. Compton
Keyword(s):  
Diffusion Coefficients ◽  
Reaction Mechanisms ◽  
Variable Temperature ◽  
Electrode Reaction

Rotating disc electrodes: the theory of chronoamperometry and its use in mechanistic investigations

1988 ◽  
Vol 418 (1854) ◽  
pp. 113-154 ◽  
Keyword(s):  
Diffusion Coefficients ◽  
Reaction Mechanisms ◽  
Electrode Reaction ◽  
Rotating Disc ◽  
Potential Step ◽  
Wide Range ◽  
Mechanistic Investigations ◽  
Disc Electrodes ◽  
Theoretical Results ◽  
Computational Strategy

A general computational strategy is presented for the calculation of the chronoamperometric responses arising from potential-step experiments at rotating disc electrodes. The method is applicable to a wide range of electrode reaction mechanisms and theoretical results are given for single- and double-potential-step experiments for ECE, DISP1, DISP2, EC' and CE reactions. For the last, the treatment is extended to cover the case where reactants have grossly unequal diffusion coefficients. Steadystate behaviour is also deduced. The extent to which the various mechanistic pathways can be distinguished is identified and the necessary experiments defined.

Application of microelectrodes and variable-temperature techniques to voltammetric studies of inorganic reaction mechanisms

1989 ◽  
Vol 93 (1) ◽  
pp. 1-18 ◽  
Author(s):  
C.D. Baer ◽  
T.F. Camaioni-Neto ◽  
D.A. Sweigart ◽  
A.M. Bond ◽  
T.F. Mann ◽  
...  
Keyword(s):  
Reaction Mechanisms ◽  
Variable Temperature ◽  
Voltammetric Studies

Automatically Identifying Electrode Reaction Mechanisms Using Deep Neural Networks

2019 ◽  
Vol 91 (19) ◽  
pp. 12220-12227 ◽  
Author(s):  
Gareth F. Kennedy ◽  
Jie Zhang ◽  
Alan M. Bond
Keyword(s):  
Neural Networks ◽  
Reaction Mechanisms ◽  
Deep Neural Networks ◽  
Electrode Reaction

Electrode reaction mechanisms of platinum isocyanide complexes in acetonitrile solutions

1988 ◽  
Vol 33 (11) ◽  
pp. 1489-1492 ◽  
Author(s):  
Katsuo Takahashi ◽  
Yasuhiro Yamamoto ◽  
Kiyoshi Matsuda ◽  
Hiroshi Yamazaki
Keyword(s):  
Reaction Mechanisms ◽  
Electrode Reaction ◽  
Acetonitrile Solutions

scholarly journals Diradical reaction mechanisms in [3 + 2]-cycloadditions of hetaryl thioketones with alkyl- or trimethylsilyl-substituted diazomethanes

2016 ◽  
Vol 12 ◽  
pp. 716-724 ◽  
Author(s):  
Grzegorz Mlostoń ◽  
Paulina Pipiak ◽  
Heinz Heimgartner
Keyword(s):  
Reaction Mechanisms ◽  
Variable Temperature ◽  
Single Case ◽  
Trimethylsilyl Diazomethane ◽  
Cascade Processes ◽  
Higher Temperature

Reactions of dihetaryl and aryl/hetaryl thioketones with 2-diazopropane, diazoethane, and (trimethylsilyl)diazomethane were studied at variable temperature. The experiments showed that reactions with 2-diazopropane carried out at –75 °C occur mainly via the initially formed, relatively stable 1,3,4-thiadiazolines as products of the [3 + 2]-cycloaddition of the diazo dipole onto the C=S bond. The latter decompose only at higher temperature (ca. −40 °C) to generate thiocarbonyl S-isopropanide. In the absence of the starting thioketone, the corresponding thiiranes and/or ethene derivatives, formed from them via spontaneous desulfurization, are the main products. In contrast, reactions with diazoethane occurred predominantly via initially formed diradicals, which in cascade processes gave sterically crowded 4,4,5,5-tetrahetaryl-1,3-dithiolanes as major products. Finally, the reaction of dihetaryl thioketones with (trimethylsilyl)diazomethane occur smoothly at −75 °C leading to the corresponding 4,4,5,5-tetrahetaryl-1,3-dithiolanes as the exclusive [3 + 2]-cycloadducts formed via a cascade of postulated diradicals. The presence of S or Se atoms in the hetaryl rings is of importance for stabilizing diradical intermediates. Remarkably, in no single case, the ‘head-to-head dimerization’ of aryl/hetaryl and dihetaryl substituted thiocarbonyl ylides was observed.

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