Monomer and polymer solvent dynamic control of an electron-transfer cross-reaction rate at a redox polymer/solution interface

1991 ◽  
Vol 113 (14) ◽  
pp. 5183-5187 ◽  
Author(s):  
Honghua Zhang ◽  
Royce W. Murray
Keyword(s):  
Electron Transfer ◽  
Polymer Solution ◽  
Reaction Rate ◽  
Dynamic Control ◽  
Cross Reaction ◽  
Redox Polymer ◽  
Solution Interface ◽  
Polymer Solvent

The dehydrogenation of 1,4-dihydronaphthalene by tetrachloro-p-benzoquinone

1976 ◽  
Vol 54 (14) ◽  
pp. 2261-2265 ◽  
Author(s):  
Z. M. Hashish ◽  
I. M. Hoodless
Keyword(s):  
Electron Transfer ◽  
Charge Transfer ◽  
Reaction Rate ◽  
Second Order ◽  
Charge Transfer Complexes ◽  
Ion Transfer ◽  
Hydride Ion ◽  
Rate Determining Step ◽  
Hydride Ion Transfer

The dehydrogenation of 1,4-dihydronaphthalene by tetrachloro-p-benzoquinone in phenetole solution has been investigated. The present work does not fully confirm earlier studies which report that the reaction follows second-order kinetics and that the hydride ion transfer is rate determining. In the investigations described in this paper second-order kinetics are only observed in the later stages of the reaction and a 1:1 stoichiometry of the reactants in the process is not obtained. Substitution of tritium in the 1,4-positions of the hydrocarbon appears to not significantly affect the reaction rate. The present results indicate that charge-transfer complexes are formed in the reaction and it is suggested that electron transfer within these complexes could be the rate-determining step in the dehydrogenation.

Concerted double proton-transfer electron-transfer between catechol and superoxide radical anion

2017 ◽  
Vol 19 (38) ◽  
pp. 26179-26190 ◽  
Author(s):  
Jorge Quintero-Saumeth ◽  
David A. Rincón ◽  
Markus Doerr ◽  
Martha C. Daza
Keyword(s):  
Electron Transfer ◽  
Proton Transfer ◽  
Superoxide Anion ◽  
Radical Anion ◽  
Reaction Rate ◽  
Superoxide Radical ◽  
Superoxide Radical Anion ◽  
Double Proton Transfer

Catechol reacts with a superoxide anion via concerted double proton-transfer electron-transfer with a reaction rate that is dominated by tunneling.

Volumes of activation for electrode processes of various charge-types in nonaqueous solvents

2001 ◽  
Vol 79 (12) ◽  
pp. 1864-1869 ◽  
Author(s):  
Mitsuru Matsumoto ◽  
Delanie Lamprecht ◽  
Michael R North ◽  
Thomas W Swaddle
Keyword(s):  
Electron Transfer ◽  
Reaction Rate ◽  
Electrode Reaction ◽  
State Theory ◽  
Exchange Reactions ◽  
Pt Electrode ◽  
Electrode Processes ◽  
Solvent Dynamics ◽  
The Mean ◽  
Dynamical Control

Volumes of activation (ΔV‡el) are reported for electron transfer at a Pt electrode of Mn(CN-cyclo-C6H11)62+/+ in acetonitrile, acetone, methanol, and propylene carbonate, and of Fe(phen)33+/2+ in acetonitrile. In all cases, ΔV‡el is markedly positive, whereas for the homogeneous self-exchange reactions of these couples in the same solvents the corresponding parameter is known to be strongly negative. The rate constants for the electrode reactions correlate loosely with the mean reactant diffusion coefficients (i.e., with solvent fluidity) and the ΔV‡el values with the volumes of activation for diffusion (i.e., for viscous flow), consistent with solvent dynamical control of the electrode reaction rate in organic solvents. A detailed analysis of ΔV‡el values of the kind presented for a couple with an uncharged member (Zhou and Swaddle, Can. J. Chem. 79, 841 (2001)) fails, however, either because of ion-pairing effects with these more highly charged couples or because of breakdown of transition-state theory in predicting the contribution of the activational barrier. Attempts to measure ΔV‡el for the oxidation of the uncharged molecule ferrocene at various electrodes in acetonitrile were unsuccessful, although ΔV‡el was again seen to be clearly positive.Key words: electrode kinetics, volumes of activation, nonaqueous electron transfer, solvent dynamics.

Estimation of Electronic Coupling for Intermolecular Electron Transfer from Cross-Reaction Data

2006 ◽  
Vol 110 (41) ◽  
pp. 11665-11676 ◽  
Author(s):  
Stephen F. Nelsen ◽  
Michael N. Weaver ◽  
Yun Luo ◽  
Jack R. Pladziewicz ◽  
Logan K. Ausman ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Cross Reaction ◽  
Electronic Coupling ◽  
Intermolecular Electron Transfer ◽  
Reaction Data
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