Outer-sphere one-electron reductions of arenediazonium salts

Doyle, Michael P.; Guy, Judith K.; Brown, Kathlynn C.; Mahapatro, Surendra N.; VanZyl, Craig M.; Pladziewicz, Jack R.

doi:10.1021/ja00239a038

Cited by 40 publications

(47 citation statements)

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“…In non-Sandmeyer (i.e. copper-free) conditions, Scheme 3 2 PERKIN outer-sphere reductions of diazonium ions by ferrocyanide in aqueous solution and by decamethylferrocene in MeCN have been reported by Doyle and co-workers 22 and we have previously inferred comparable behaviour in their reduction by Fe 2ϩ ligated by EDTA in aqueous solution at pH 9. 23 No kinetic study of Sandmeyer cyanation has been carried out, perhaps because of the formation of the intermediate solid or oily phases which have been reported for the reaction in aqueous solution.…”

supporting

confidence: 68%

Sandmeyer reactions. Part 6.1 A mechanistic investigation into the reduction and ligand transfer steps of Sandmeyer cyanation

Hanson

Rowell

Taylor

et al. 2002

J. Chem. Soc., Perkin Trans. 2

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For Sandmeyer cyanation at 298 K in 50% v/v aqueous acetonitrile buffered at pH 8, absolute rate constants have been obtained for the reduction of 4-methoxybenzenediazonium tetrafluoroborate by the cyanocuprate() anions Cu  (CN) 4 3Ϫ , Cu  (NCMe)(CN) 3 2Ϫ and Cu  (NCMe) 2 (CN) 2 Ϫ as (0.50 ± 0.05), (0.12 ± 0.03) and 0.0 dm 3 mol Ϫ1 s Ϫ1 , respectively. The relative reactivity of the two reactive cyanocuprates reflects the estimated difference in their standard reduction potentials. Ligand transfer to the aryl radical from the cyanocuprate() anions produced in the reaction occurs within the solvent cage. By use of radical clocks, first order rate constants of the order of 1 × 10 8 s Ϫ1 for ligand transfer between the caged reactants can be evaluated although the transfer rate may vary from one aryl radical to another. No difference was discerned in ligand transferring reactivity between the two cyanocuprate() complexes involved.

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supporting

confidence: 68%

Sandmeyer reactions. Part 6.1 A mechanistic investigation into the reduction and ligand transfer steps of Sandmeyer cyanation

Hanson

Rowell

Taylor

et al. 2002

J. Chem. Soc., Perkin Trans. 2

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“…An estimation of the rate constant for this Electron Transfer (ET) step can be obtained through Marcus' equations. [49,58,59] The calculated value of 1.9 * 10 6 M -1 sec -1 for k i is consistent with our initial hypothesis on an acceptable role for 1-glycerolate.…”

Section: Scheme 1 Dissociation Of 1asupporting

confidence: 87%

“…This unexpected decomposition of the diazonium salt 1 in Gly/KF DES could represent a transition metal-free and green strategy of hydrodediazoniation of arenediazonium compounds, otherwise carried out in boiling ethanol [47,48] with relatively complex catalytic systems [49,50] or, in any case, in classical volatile organic solvents. [51,52] More interestingly, it represents a measure of the background reactivity of such compounds in DESs, and this prompted us to try to elucidate the involved mechanism.…”

Section: Investigation and Elucidation Of The Reaction Mechanismmentioning

confidence: 92%

How do arenediazonium salts behave in deep eutectic solvents? A combined experimental and computational approach

Antenucci

Bonomo

Ghigo

et al. 2021

Journal of Molecular Liquids

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“…In view of the significant uncertainties associated to the proposed model due to the assumed controversial data, an experimental validation of the redox nature of the inhibition reaction was conducted by replacing DPPH by various electro‐reducible molecules for which E 0 < E 0 4‐NBD . For this purpose, tetrachloro‐1,4‐benzoquinone (chloranil), which is reversibly reduced into its corresponding semiquinone at E 0 Cloranil =−0.33 V vs .…”

Section: Introductionmentioning

confidence: 99%

Diazonium Grafting Control through a Redox Cross‐Reaction: Elucidation of the Mechanism Involved when using 2,2‐Diphenylpicrylhydrazyl as an Inhibitor

et al. 2018

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Investigation into the mechanism involved in the control of layer growth through the reduction of diazonium salts by using 2,2-diphenylpicrylhydrazyl (DPPH). This approach, previously assumed to be based on the radical capture of highly reactive aryl intermediates via the scavenging activity of DPPH, actually rests on redox cross reactions involving its electro-reduced form. A numerical approach was developed to model the proposed processes, involving a redox reaction between diazonium cations and the reduced species of DPPH as a central step. Extension of this approach was validated by using substituted benzoquinones instead of DPPH, leading to good control of the radical polymerization to give sub-monolayer surface coverage. Modulation of the surface coverage can be obtained by adjusting the concentration of the redox mediator and a near-monolayer can be prepared in this way. The difference in formal redox potential between the diazonium salt and the electro-reducible mediator was identified as a key parameter, and could be exploited to generalize the grafting control.

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Outer-sphere one-electron reductions of arenediazonium salts

Cited by 40 publications

References 0 publications

Sandmeyer reactions. Part 6.1 A mechanistic investigation into the reduction and ligand transfer steps of Sandmeyer cyanation

Sandmeyer reactions. Part 6.1 A mechanistic investigation into the reduction and ligand transfer steps of Sandmeyer cyanation

How do arenediazonium salts behave in deep eutectic solvents? A combined experimental and computational approach

Diazonium Grafting Control through a Redox Cross‐Reaction: Elucidation of the Mechanism Involved when using 2,2‐Diphenylpicrylhydrazyl as an Inhibitor

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