Modification of carbon surfaces with methyl groups by using ferrocene derivatives as redox catalysts of the oxidation of acetate ions

Hernández-Muñoz, Lindsay S.; Fragoso‐Soriano, Rogelio; Vázquez-López, C.; Klimova, Elena I.; Ortiz‐Frade, Luis; Astudillo, Pablo D.; González, Felipe J.

doi:10.1016/j.jelechem.2010.09.006

Cited by 18 publications

(11 citation statements)

References 25 publications

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“…Ferrocene and decamethylferrocene act as redox catalysts in Meerwein arylation reactions [ 29 ], borylations of arenediazonium salts [ 30 ] and in C–H imidation reactions of (hetero)arenes [ 31 ] ( Scheme 1 ,c). Ferrocene has been used as redox mediator for the electrochemical modification of carbon surfaces via electrochemical oxidation of carboxylates [ 32 – 33 ], as mediator for dehydrogenative coupling reactions [ 34 – 35 ] and for olefin hydroamidations [ 36 ] ( Scheme 1 –f).…”

Section: Introductionmentioning

confidence: 99%

Polysubstituted ferrocenes as tunable redox mediators

Waniek¹,

Klett²,

Förster³

et al. 2018

Beilstein J. Org. Chem.

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A series of four ferrocenyl ester compounds, 1-methoxycarbonyl- (1), 1,1’-bis(methoxycarbonyl)- (2), 1,1’,3-tris(methoxycarbonyl)- (3) and 1,1’,3,3’-tetrakis(methoxycarbonyl)ferrocene (4), has been studied with respect to their potential use as redox mediators. The impact of the number and position of ester groups present in 1–4 on the electrochemical potential E 1/2 is correlated with the sum of Hammett constants. The 1/1 +–4/4 + redox couples are chemically stable under the conditions of electrolysis as demonstrated by IR and UV–vis spectroelectrochemical methods. The energies of the C=O stretching vibrations of the ester moieties and the energies of the UV–vis absorptions of 1–4 and 1 +–4 + correlate with the number of ester groups. Paramagnetic 1H NMR redox titration experiments give access to the chemical shifts of 1 +–4 + and underline the fast electron self-exchange of the ferrocene/ferrocenium redox couples, required for rapid redox mediation in organic electrosynthesis.

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Section: Introductionmentioning

confidence: 99%

Polysubstituted ferrocenes as tunable redox mediators

Waniek¹,

Klett²,

Förster³

et al. 2018

Beilstein J. Org. Chem.

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“…The main features of this behavior have been previously explained and is due to the intervention of a redox catalyst mechanism (Scheme ), which promotes the valerate decarboxylation and the generation of n‐butyl radicals, whose reaction with the carbon surface and blocking of this one is evidenced by the decrease of the oxidation peak during successive cycles (Figure D). In this experiment, five cycles were required to reach a totally inhibited state of the electrode and the starting surface was never recovered by ultrasonic rinsing in several solvents, which means that the cycling procedure gave rise to a covalently modified surface.…”

Section: Resultsmentioning

confidence: 68%

“…To prepare the modified carbon surface with saturated alkyl chains, the oxidation of tetrabutylammonium valerate was performed. Due to the fact that electrografting cannot be carried out by direct oxidation of this carboxylate, a procedure using ferrocenecarboxaldehyde as redox catalyst was used . Figure A shows the voltammetric behavior of the above mentioned carboxylate ( E p =1.16 V/SCE at 0.1 V s −1 ), which does not present any electrode inhibition effect .…”

Section: Resultsmentioning

confidence: 99%

Hydrogen Bonding Effects on the Reversible Reorganization of Organic Films Electrografted on Glassy Carbon Electrodes

Morales-Martínez

González

2018

ChemElectroChem

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The electrochemical oxidation of tetrabutylammonium carboxylates derived from 6‐oxoheptanoic acid and 6‐heptynoic acid was performed on glassy carbon electrodes to generate covalently modified electrodes bearing alkyl‐ketone and alkynyl groups. These surfaces were used as models of hydrogen‐bond‐accepting surfaces to study the interaction of water with the grafted film; 1,4‐benzoquinone was used as the redox probe to demonstrate the existence of these interactions. The voltammetric behavior of this redox probe on the modified electrode changed during cycling. However, leaving this electrode to stand in the electrolyte solution allows the recovery of the starting voltammogram. These changes observed between cycling and stand time are cyclical and can be explained through a reversible reorganization effect of the grafted film, which is attributed to hydrogen bonding interactions between the functional groups present in the structure film and water present in the solvent. Supporting these surface effects, the switching behavior was absent on hydrophobic films formed with saturated aliphatic chains or by using ferrocene as non‐hydrogen bonding redox probe.

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“…The modification of glassy carbon electrodes was performed by oxidation of 4‐(4‐nitrophenyl)butyrate (NO 2 Ph(CH 2 ) 3 COO − ), using ferrocenecarboxaldehyde (FcCHO) as redox catalyst. This procedure was previously used to functionalize carbon surfaces by mediated oxidation of acetate and nitrophenylacetate ions in acetonitrile solution, whose general mechanism was adapted here for the case of the 4‐(4‐nitrophenyl)butyrate (Scheme ). The sequence of reactions involves first the oxidation of the ferrocenecarboxaldehyde (FcCHO) to yield the respective ferrocenium derivative (Fc + CHO), which exchange one electron with a carboxylate molecule (NO 2 Ph(CH 2 ) 3 COO − ) to generate an acyloxy radical (NO 2 Ph(CH 2 ) 3 COO .…”

Section: Resultsmentioning

confidence: 99%

Effect of Electrolyte Ions on the Formation, Electroactivity, and Rectification Properties of Films Obtained by Electrografting

2019

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The oxidation of 4‐(4‐nitrophenyl)butyrate ions in acetonitrile was used to modify glassy carbon surfaces with films bearing 3‐(4‐nitrophenyl)propyl groups. The main features of the voltammetric reduction of the grafted nitrophenyl groups were studied in two different supporting electrolytes; n‐Bu4NPF6 and Me4NPF6. The best response was obtained with the less bulky electrolyte, which was explained by the major capability of these ions to diffuse inside the channels of the grafted film, as well as the better stabilization of the radical anions generated during the reduction process. It was also shown that the films electrografted in presence of the bulky n‐Bu4NPF6 are thicker but less compact than those prepared in Me4NPF6. The amount of nitrophenyl groups in the grafted film that can be reduced depends on the size of the electrolyte ions. The permeation of the electrolyte ions inside the film channels determines also the voltammetric behavior of ferrocene as redox probe. A current rectification phenomenon was observed in acetonitrile solutions of bulky and hydrophobic electrolytes like n‐Bu4NPF6 and n‐Hx4NPF6, whose marginal inclusion inside the film channels promotes both the entrance of ferrocene and the expelling of ferrocenium ions from these ones. This phenomenon was emulated through a CEC mechanism in solution, where the diffusion inside the channels was described as single chemical equilibria.

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Modification of carbon surfaces with methyl groups by using ferrocene derivatives as redox catalysts of the oxidation of acetate ions

Cited by 18 publications

References 25 publications

Polysubstituted ferrocenes as tunable redox mediators

Polysubstituted ferrocenes as tunable redox mediators

Hydrogen Bonding Effects on the Reversible Reorganization of Organic Films Electrografted on Glassy Carbon Electrodes

Effect of Electrolyte Ions on the Formation, Electroactivity, and Rectification Properties of Films Obtained by Electrografting

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