Kinetics of the reduction of cytochrome c by [FeII(edta)(H2O)]2−: outer-sphere vs. inner-sphere electron transfer mechanisms

2003 ◽  
pp. 2704-2709 ◽  
Author(s):  
Joanna Macyk ◽  
Rudi van Eldik
Keyword(s):  
Electron Transfer ◽  
Cytochrome C ◽  
Outer Sphere ◽  
Inner Sphere ◽  
Kinetics Of ◽  
Transfer Mechanisms

Electron transfer kinetics of cobaloxime complexes

1996 ◽  
Vol 74 (5) ◽  
pp. 658-665 ◽  
Author(s):  
Kefei Wang ◽  
R.B. Jordan
Keyword(s):  
Electron Transfer ◽  
Exchange Rate ◽  
Rate Constants ◽  
Ph Dependence ◽  
Outer Sphere ◽  
The Self ◽  
Oxidation Of Co ◽  
Reduction Potentials ◽  
Inner Sphere ◽  
Kinetics Of

The rates of oxidation of CoII(dmgBF2)2(OH2)2 by CoIII(NH3)5X2+ (X = Br−, Cl−, and N3−) have been studied at 25 °C in 0.10 M LiClO4. The rate constants are 50 ± 9, 2.6 ± 0.2, and 5.9 ± 1.0 M−1 s−1 for X = Br−, Cl−, and N3−, respectively, in 0.01 M acetate buffer at pH 4.7. The relative rates are consistent with the inner-sphere bridging mechanism established earlier by Adin and Espenson for the analogous reactions of CoII(dmgH)2(OH2)2. The rate constants with CoII(dmgBF2)2(OH2)2 typically are ~103 times smaller and this is attributed largely to the smaller driving force for the CoII(dmgBF2)2(OH2)2 complex. The outer-sphere oxidations of cobalt(II) sepulchrate by CoIII(dmgH)2(OH2)2+ (pH 4.76–7.35, acetate, MES, and PIPES buffers) and CoIII(dmgBF2)2(OH2)2+ (pH 3.3–7.42, chloroacetate, acetate, MES, and PIPES buffers) have been studied. The pH dependence gives the following rate constants (M−1 s−1) for the species indicated: (1.55 ± 0.09) × 105 (CoIII(dmgBF2)2(OH2)2+); (5.5 ± 0.3) × 103 (CoII(dmgH)2(OH2)2+); (3.1 ± 0.5) × 102 (CoIII(dmgH)2(OH2)(OH)); (2.5 ± 0.3) × 102 (CoIII(dmgBF2)2(OH2)(OH)). The known reduction potentials for cobalt(III) sepulchrate and the diaqua complexes, and the self-exchange rate for cobalt(II/III) sepulchrate, are used to estimate the self-exchange rate constants for the dioximate complexes. Comparisons to other reactions with cobalt sepulchrate indicates best estimates of the self-exchange rate constants are ~2.4 × 10−2 M−1 s−1 for CoII/III(dmgH)2(OH2)2and ~5.7 × 10−3 M−1 s−1 for CoII/III(dmgBF2)2(OH2)2. Key words: electron transfer, cobaloxime, inner sphere, outer sphere, self-exchange.

Resolving the kinetics of individual aqueous reaction steps of actinyl (AnO2+ and AnO22+; An=U, Np, and Pu) tricarbonate complexes with ferrous iron and hydrogen sulfide from first principles

2020 ◽  
Vol 108 (3) ◽  
pp. 165-184
Author(s):  
Will M. Bender ◽  
Udo Becker
Keyword(s):  
Electron Transfer ◽  
Proton Transfer ◽  
Outer Sphere ◽  
Future Research ◽  
Inner Sphere ◽  
Proton Transfer Reactions ◽  
Effective Shield ◽  
Sphere Complex ◽  
Solvent Molecules ◽  
Kinetics Of

AbstractThe solubility and mobility of actinides (An), like uranium, neptunium, and plutonium, in the environment largely depends on their oxidation states. Actinyls (AnV,VIO2+/2+(aq)) form strong complexes with available ligands, like carbonate (CO32−), which may inhibit reduction to relatively insoluble AnIVO2(s). Here we use quantum-mechanical calculations to explore the kinetics of aqueous homogeneous reaction paths of actinyl tricarbonate complexes ([AnO2(CO3)3]5−/4−) with two different reductants, [Fe(OH)2(H2O)4]0 and [H2S(H2O)6]0. Energetically-favorable outer-sphere complexes (OSC) are found to form rapidly, on the order of milliseconds to seconds over a wide actinyl concentration range (pM to mM). The systems then encounter energy barriers (Ea), some of which are prohibitively high (>100 kJ/mol for some neptunyl and plutonyl reactions with Fe2+ and H2S), that define the transition from outer- to inner-sphere complex (ISC; for example, calculated Ea of ISC formation between UO2+ and UO22+ with Fe2+ are 35 and 74 kJ/mol, respectively). In some reactions, multiple OSCs are observed that represent different hydrogen bonding networks between solvent molecules and carbonate. Even when forming ISCs, electron transfer to reduce An6+ and An5+ is not observed (no change in atomic spin values or lengthening of An–Oax bond distances). Proton transfer from bicarbonate and water to actinyl O was tested as a mechanism for electron transfer from Fe2+ to U6+ and Pu6+. Not all proton transfer reactions yielded reduction of An6+ to An5+ and only a few pathways were energetically-favorable (e. g. H+ transfer from H2O to drive Pu6+ reduction to Pu5+ with ΔE = −5 kJ/mol). The results suggest that the tricarbonate complex serves as an effective shield against actinide reduction in the tested reactions and will maintain actinyl solubility at elevated pH conditions. The results highlight reaction steps, such as inner-sphere complex formation and electron transfer, which may be rate-limiting. Thus, this study may serve as the basis for future research on how they can be catalyzed by a mineral surface in a heterogeneous process.

scholarly journals RuIII(edta) complexes as molecular redox catalysts in chemical and electrochemical reduction of dioxygen and hydrogen peroxide: inner-sphere versus outer-sphere mechanism

RSC Advances ◽  
2021 ◽  
Vol 11 (35) ◽  
pp. 21359-21366
Author(s):  
Debabrata Chatterjee ◽  
Marta Chrzanowska ◽  
Anna Katafias ◽  
Maria Oszajca ◽  
Rudi van Eldik
Keyword(s):  
Hydrogen Peroxide ◽  
Electron Transfer ◽  
Electrochemical Reduction ◽  
Molecular Oxygen ◽  
Outer Sphere ◽  
Transfer Processes ◽  
Edta Complexes ◽  
Inner Sphere ◽  
Electron Transfer Processes ◽  
Sphere Mechanism

[RuII(edta)(L)]2–, where edta4– =ethylenediaminetetraacetate; L = pyrazine (pz) and H2O, can reduce molecular oxygen sequentially to hydrogen peroxide and further to water by involving both outer-sphere and inner-sphere electron transfer processes.

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