Linear sweep voltammetry: Kinetic control by charge transfer and/or secondary chemical reactions

Nadjo, Louis; Savéant, Jean‐Michel

doi:10.1016/s0022-0728(73)80300-6

Cited by 414 publications

(179 citation statements)

References 12 publications

Supporting

Mentioning

164

Contrasting

Order By: Relevance

“…Moreover, the ratio of anodic/cathodic peak current is less than unity and gradually increases to approximate I pa / I pc =1 at higher υ values. These diagnostic criteria indicate an electron-transfer process with a coupled homogeneous chemical-reaction step (EC mechanism)16, 17 that follows first-order kinetics (−30 mV shift of E pc with Δlog υ= 1 and n =1 at 298 K).…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of Redox‐Active Charge‐Transfer Complexes with 2,3,5,6‐Tetracyanopyridine (TCNPy) for the Photogeneration of Pyridinium Radicals

Wöß

Monkowius

Knör

2012

Chemistry A European J

View full text Add to dashboard Cite

The heteroaromatic polynitrile compound tetracyanopyridine (TCNPy) is introduced as a new electron acceptor for the formation of deeply colored charge-transfer complexes. In MeCN, TCNPy is characterized by a quasireversible one-electron-reduction process at −0.51 V (versus SCE). The tetracyanopyridine radical anion undergoes a secondary chemical reaction, which is assigned to a protonation step. TCNPy has been demonstrated to generate 1:1 complexes with various electron donors, including tetrathiafulvalene (TTF) and dihydroxybenzene derivatives, such as p-hydroquinone and catechol. Visible- or NIR-light-induced excitation of the intense charge-transfer bands of these compounds leads to a direct optical electron-transfer process for the formation of the corresponding radical-ion pairs. The presence of available electron donors that contain protic groups in close proximity to the TCNPy acceptor site opens up a new strategy for the photocontrolled generation of pyridinium radicals in a stepwise proton-coupled electron-transfer (PCET) sequence.

show abstract

Section: Resultsmentioning

confidence: 99%

Synthesis and Characterization of Redox‐Active Charge‐Transfer Complexes with 2,3,5,6‐Tetracyanopyridine (TCNPy) for the Photogeneration of Pyridinium Radicals

Wöß

Monkowius

Knör

2012

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…The peak potential (E p ) varies linearly with the logarithm of the scan rate by -74 mV/dec with a peak width E p/2 -E p = 68 mV. These values correspond to an electron transfer followed by a chemical reaction (EC, E -electrochemical and C-chemical) scheme, with a mixed kinetic control by the E and C steps [13,14]. This reaction sequence may be also evidenced by other experimental observations: (I) the appearance of several anodic waves if the scan is stopped after the second wave, suggesting the oxidation of the products formed after the second reduction step ( Fig.…”

Section: Cyclic Voltammetrymentioning

confidence: 99%

Electrochemical study and MO — modeling of the reduction behaviour of some arylidene substituted derivatives of dibenz [b,e]-thiepin-5,5-dioxide-11-one

Preda

Volanschi

2009

Open Chemistry

View full text Add to dashboard Cite

The electrochemical reduction of four arylidene substituted derivatives of dibenz-[b,e]-thiepin-5,5-dioxide-11-one has been studied by cyclic voltammetry on platinum (Pt) electrode in aprotic media (DMSO), coupled with spectral EPR techniques. From the analysis of cyclic voltammetry experiments, aided by digital simulations using DigiSim software, the kinetic and thermodynamic parameters were evaluated for each system. The electrochemical behaviour is strongly directed by the nature of the arylidene substituents bound to the central heterocycle. The electrochemical investigation and solvent dependent semiempirical modeling using the PM3 hamiltonian in the frame of AMPAC program package allowed a rationalisation of experimental data regarding the electrochemical reduction and the reactivity of the intermediate species involved.© Versita Warsaw and Springer-Verlag Berlin Heidelberg.

show abstract

“…[16,17,18] More trumpet plots covering the whole pH range can be seen in the Supporting Information. The results obtained in this way at all available pH values are reported in Figure 5.…”

Section: Introductionmentioning

confidence: 99%

Concerted and Stepwise Proton‐Coupled Electron Transfers in Aquo/Hydroxo Complex Couples in Water: Oxidative Electrochemistry of [Os^II(bpy)₂(py)(OH₂)]²⁺

et al. 2009

View full text Add to dashboard Cite

Successive oxidation of transition metal(II) aqua complexes (M(II)OH(2) to M(III)OH) is a domain in which proton-coupled electron transfer reactions are extremely common. The mechanism of these PCET reactions-concerted or stepwise-is an important issue in the understanding and design of natural or artificial systems catalyzing the formation of dioxygen by four-electron oxidation of water. Concerted proton-coupled electron transfer from an aqua metal(II) to a hydroxo metal(III) complex requires the close proximity of a proton-accepting group with a pK value between those of the aqua complexes. Otherwise, stepwise electron-proton or proton-electron pathways involving high-energy intermediates are followed. Concerted proton-electron pathways involving water as proton-acceptor or proton-donor group are inefficient. Cyclic voltammetry of the title complex in buffered aqueous solution and re-examination of previous results for the same complex attached to an electrode surface are used to establish these conclusions, which provide a starting point on the route to higher degrees of oxidation, such as those involved in the catalysis of water oxidation.

show abstract

Linear sweep voltammetry: Kinetic control by charge transfer and/or secondary chemical reactions

Cited by 414 publications

References 12 publications

Synthesis and Characterization of Redox‐Active Charge‐Transfer Complexes with 2,3,5,6‐Tetracyanopyridine (TCNPy) for the Photogeneration of Pyridinium Radicals

Synthesis and Characterization of Redox‐Active Charge‐Transfer Complexes with 2,3,5,6‐Tetracyanopyridine (TCNPy) for the Photogeneration of Pyridinium Radicals

Electrochemical study and MO — modeling of the reduction behaviour of some arylidene substituted derivatives of dibenz [b,e]-thiepin-5,5-dioxide-11-one

Concerted and Stepwise Proton‐Coupled Electron Transfers in Aquo/Hydroxo Complex Couples in Water: Oxidative Electrochemistry of [Os^II(bpy)₂(py)(OH₂)]²⁺

Contact Info

Product

Resources

About

Linear sweep voltammetry: Kinetic control by charge transfer and/or secondary chemical reactions

Cited by 414 publications

References 12 publications

Synthesis and Characterization of Redox‐Active Charge‐Transfer Complexes with 2,3,5,6‐Tetracyanopyridine (TCNPy) for the Photogeneration of Pyridinium Radicals

Synthesis and Characterization of Redox‐Active Charge‐Transfer Complexes with 2,3,5,6‐Tetracyanopyridine (TCNPy) for the Photogeneration of Pyridinium Radicals

Electrochemical study and MO — modeling of the reduction behaviour of some arylidene substituted derivatives of dibenz [b,e]-thiepin-5,5-dioxide-11-one

Concerted and Stepwise Proton‐Coupled Electron Transfers in Aquo/Hydroxo Complex Couples in Water: Oxidative Electrochemistry of [OsII(bpy)2(py)(OH2)]2+

Contact Info

Product

Resources

About

Concerted and Stepwise Proton‐Coupled Electron Transfers in Aquo/Hydroxo Complex Couples in Water: Oxidative Electrochemistry of [Os^II(bpy)₂(py)(OH₂)]²⁺