Decomposition of the ferricenium cation by nucleophilic reagents

Prins, R.; Korswagen, A. R.; Kortbeek, A.G.T.G.

doi:10.1016/s0022-328x(00)80459-3

Cited by 169 publications

(110 citation statements)

References 26 publications

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“…Fc groups leading to conversion of 3Fc + to FeCl4 -and 2Fc as noted elsewhere by UV-visible spectroscopy of oxidized ferrocene [12,13]. Whatever the reason, it is clear that Cl -induces a loss of Fc reactivity at electrode surfaces subjected to repetitive CV cycling, which is electrochemically non-labile and/or non-reducible to ethynyl Fc during the reverse cathodic scan (Fig.…”

Section: Studies In Organic Solventsupporting

confidence: 60%

Electrochemical Mechanism of Ferrocene-Based Redox Molecules in Thin Film Membrane Electrodes

Cuartero

Acres

Bradley

et al. 2017

Electrochimica Acta

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2 GRAPHICAL ABSTRACTCartoon illustrating NaCl permeation through water nanodroplets and Cl -exchange at the membrane/sample interface, both of which create an environment to enable the formation of FeCln 3-n complexes, leading to a non-reversibility in the redox chemistry of the membrane. RESEARCH HIGHLIGHTS electrochemistry of ferrocene derivatives in polymeric membranes  role of chloride on the irreversible oxidation of ferrocene in thin film membranes  synchrotron radiation study of chloride on the ferrocene reactivity in membranes  elimination of chloride induced irreversibility of the ferrocene reaction chemistry ABSTRACTCyclic voltammetry (CV) in chloride-based aqueous electrolytes of ferrocene molecule doped thin membranes (~200 nm in thickness) on glassy carbon (GC) substrate electrodes, both plasticized poly(vinyl chloride) (PVC) and unplasticized poly(methyl methacrylate)/poly(decyl methacrylate) (PMMA-PDMA) membranes, has shown that the electrochemical oxidation behavior is irreversible due most likely to 3 degradation of ferrocene at the buried interface (GC|membrane). Furthermore, CV of the ferrocene molecules at GC electrodes in organic solvents employing chloride-based and chloride-free organic electrolytes has demonstrated that the chloride anion is inextricably linked to this irreversible ferrocene oxidation electrochemistry. Accordingly, we have explored the electrochemical oxidation mechanism of ferrocenebased redox molecules in thin film plasticized and unplasticized polymeric membrane electrodes by coupling synchrotron radiation-X-ray photoelectron spectroscopy (SR-XPS) and near edge X-ray absorption fine structure (NEXAFS) with argon ion sputtering to depth profile the electrochemically oxidized thin membrane systems. With the PVC depth profiling studies, it was not possible to precisely study the influence of chloride on the ferrocene reactivity due to the high atomic ratio of chloride in the PVC membrane; however, the depth profiling results obtained with a chlorine-free polymer (PMMA-PDMA) provided irrefutable evidence for the formation of a chloride-based iron product at the GC|PMMA-PDMA interface. Finally, we have identified conditions that prevent the irreversible conversion of ferrocene by utilizing a high loading of redox active reagent and/or an ionic liquid (IL) membrane plasticizer with high ionicity that suppresses the mass transfer of chloride.

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Section: Studies In Organic Solventsupporting

confidence: 60%

Electrochemical Mechanism of Ferrocene-Based Redox Molecules in Thin Film Membrane Electrodes

Cuartero

Acres

Bradley

et al. 2017

Electrochimica Acta

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“…These results are in contrast to earlier reports that ferricinium is rapidly decomposed in dimethylsulfoxide and dimethylformamide. 10 However, we observed that ferricinium decomposes in hexamethylphosphoramide even on the cyclic voltammetric timescale, as evidenced by reverse (cathodic-going) voltametric peaks that were markedly smaller than the forward anodic peaks in this solvent using ferrocene as the solute. -- Criss and Salomon 1 4 , 1 5 have analyzed the available data for the ionic entropies S 0 of simple univalent cations in various solvents in terms of the structural properties of the solvent.…”

Section: Methodsmentioning

confidence: 78%

Deficiencies of the ferricinium-ferrocene redox couple for estimating transfer energies of single ions

Sahami

Weaver

1981

J Solution Chem

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“…The electrolyte was a 1.0 m aqueous solution of perchloric acid, so as to comply with the general procedures in this particular field. [7,8] This has the advantage of being a highly conductive ionic solution that does not give rise to www.chemphyschem.org ferrocenium ion decomposition, [74][75][76] while containing perchlorate anions which stabilize the electrogenerated ferrocenium by ion pairing. [58,67] All electrolyte solutions were rigorously purged with argon to prevent any reaction between the electrogenerated ferrocenium cation and residual molecular oxygen.…”

Section: Methodsmentioning

confidence: 99%

Ultrafast Voltammetry for Probing Interfacial Electron Transfer in Molecular Wires

et al. 2007

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Electron transfer inside self-assembled monolayers made from complex redox-active oligophenylenevinylene molecular wires is examined by ultrafast cyclic voltammetry. Rate constants above 10(6) s(-1) are measured when the electroactive moieties are easily accessible to counterions from the electrolyte. These counterion movements are necessary to compensate the local charge created upon electron transfer. Conversely, if the redox center is buried within long hydrophobic diluents, the counterion movement towards the redox entity becomes rate limiting, thus drastically altering the rate magnitude and its physical meaning. This change in the mechanism is examined both for superexchange or when one electron-hopping step is involved.

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Decomposition of the ferricenium cation by nucleophilic reagents

Cited by 169 publications

References 26 publications

Electrochemical Mechanism of Ferrocene-Based Redox Molecules in Thin Film Membrane Electrodes

Electrochemical Mechanism of Ferrocene-Based Redox Molecules in Thin Film Membrane Electrodes

Deficiencies of the ferricinium-ferrocene redox couple for estimating transfer energies of single ions

Ultrafast Voltammetry for Probing Interfacial Electron Transfer in Molecular Wires

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