RATE OF THE FERROCYANIDE-FERRICYANIDE EXCHANGE REACTION<sup>1</sup>

Wahl, Arthur C.; Deck, Charles F.

doi:10.1021/ja01644a078

Cited by 25 publications

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“…The rates are very fast with polarizable cations such as Cs + and relatively slow with less polarizable cations such as Li + or H + as the principal cations on metal electrodes such as gold (9). A similar cation effect has also been observed on the homogeneous rate constants for this couple (10). Both effects are probably a consequence of the association of the cations with the anions of the couple, particularly the ferrocyanide ion with its charge otherwise of --4 (11,12).…”

Section: Science and Technologysupporting

confidence: 67%

Redox Couple Behavior on Lithiated Nickel Oxide Electrodes

Tench

Yeager²

1974

J. Electrochem. Soc.

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The rotating electrode technique has been used to study the kinetics of various redox couples [Fe(CN)64-/Fe(CN)63-, Fe2+/Fe 3+, Cr2+/Cr 3+, and quinone/hydroquinone] on mosaic lithiated nickel oxide electrodes in sulfate solutions. At potentials cathodic to the flatband potential, the redox reactions are very inhibited. At potentials anodic to the flatband potential, the oxidation of the ferrocyanide ion exhibits a transfer coefficient of ~ : 1/2 with an apparent standard rate constant approximately two orders of magnitude smaller than on Pt. The other couples exhibit abnormal transfer coefficients under these conditions, probably because of specific adsorption on the oxide electrode surface. The kinetics of various redox reactions have been examined on lithiated mosaic nickel oxide electrodes with the objective of comparing the behavior of these couples on this compound semiconductor with that on metals. With NiO(Li) electrodes, the heterogeneous electron transfer is expected to involve rather localized valency states within the electrode phase [i.e., Ni 2+ (3d s) and Ni ~+ (3d 7) ] rather than the wide bands * Electrochemical Society Active Member. ~Present address: Fritz-Haber ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 35.8.11.2 Downloaded on 2015-06-26 to IP Vol. 121, No. 3 REDOX COUPLE BEHAVIOR ON NiO ELECTRODES 319 ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 35.8.11.2 Downloaded on 2015-06-26 to IP

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Section: Science and Technologysupporting

confidence: 67%

Redox Couple Behavior on Lithiated Nickel Oxide Electrodes

Tench

Yeager²

1974

J. Electrochem. Soc.

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“…For instance, neither [Cp 2 Fe][PF 6 ] nor [Cp 2 Fe][BPh 4 ] could be used because of their insolubility in cold THF, while reaction of 1 or 4 with [CPh 3 ][PF 6 ] resulted in formation of intractable mixtures. As a result, we have pursued the use of U(O t Bu) 6 as an “innocent” oxidant, given the ample precedent of other outer-sphere homometallic electron transfers. − U(O t Bu) 6 has several attributes which make it ideal for the proposed transformation. It is both sterically saturated and highly soluble in both aliphatic and ethereal solvents .…”

Section: Resultsmentioning

confidence: 99%

High-Valent Uranium Alkyls: Evidence for the Formation of U^VI(CH₂SiMe₃)₆

et al. 2011

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Oxidation of [Li(DME)(3)][U(CH(2)SiMe(3))(5)] with 0.5 equiv of I(2), followed by immediate addition of LiCH(2)SiMe(3), affords the high-valent homoleptic U(V) alkyl complex [Li(THF)(4)][U(CH(2)SiMe(3))(6)] (1) in 82% yield. In the solid-state, 1 adopts an octahedral geometry as shown by X-ray crystallographic analysis. Addition of 2 equiv of tert-butanol to [Li(DME)(3)][U(CH(2)SiMe(3))(5)] generates the heteroleptic U(IV) complex [Li(DME)(3)][U(O(t)Bu)(2)(CH(2)SiMe(3))(3)] (2) in high yield. Treatment of 2 with AgOTf fails to produce a U(V) derivative, but instead affords the U(IV) complex (Me(3)SiCH(2))Ag(μ-CH(2)SiMe(3))U(CH(2)SiMe(3))(O(t)Bu)(2)(DME) (3) in 64% yield. Complex 3 has been characterized by X-ray crystallography and is marked by a uranium-silver bond. In contrast, oxidation of 2 can be achieved via reaction with 0.5 equiv of Me(3)NO, producing the heteroleptic U(V) complex [Li(DME)(3)][U(O(t)Bu)(2)(CH(2)SiMe(3))(4)] (4) in moderate yield. We have also attempted the one-electron oxidation of complex 1. Thus, oxidation of 1 with U(O(t)Bu)(6) results in formation of a rare U(VI) alkyl complex, U(CH(2)SiMe(3))(6) (6), which is only stable below -25 °C. Additionally, the electronic properties of 1-4 have been assessed by SQUID magnetometry, while a DFT analysis of complexes 1 and 6 is also provided.

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