Spin trapping in electrochemistry. Nonaqueous electrochemical behavior of nitroso spin traps

Gronchi, G.; COURBIS, P.; Tordo, Paul; Mousset, G.; Simonet, Jacques

doi:10.1021/j100231a015

Cited by 31 publications

(9 citation statements)

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“…In agreement with the well-known spin-trapping ability of nitroso compounds, [31] 2-nitroso-1-naphthol (3a, A) could react with · NO 2 to give the spin adduct 13. This could subsequently evolve to the nitro derivative 9 by hydrogen abstraction and elimination of HNO, which decomposes to form H 2 O and N 2 O (Scheme 4).…”

Section: Discussionsupporting

confidence: 75%

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On the Role of Nitrogen Monoxide (Nitric Oxide) in the Nitration of a Tyrosine Derivative and Model Compounds

Giorgini¹,

Petrucci

Astolfi³

et al. 2002

Eur. J. Org. Chem.

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The nitration of tyrosine derivatives with nitrogen monoxide (nitric oxide) occurs only in the presence of dioxygen, and the hypothesized mechanism involves nitrogen dioxide (·NO2). For better understanding of the reaction mechanism, the nitration of model compounds − such as 1‐ and 2‐naphthols and their corresponding 2‐ and 1‐nitroso derivatives − with nitrogen monoxide in the presence and in the absence of dioxygen was studied. The results described here show that tyrosine and naphthols do not undergo nitrosation when they react with ·NO, and so nitrosation of tyrosine in biological systems is highly unlikely. In addition, the oxidation of nitrosonaphthols ←⇄ isonitrosonaphthols by nitric oxide and its derivatives to the corresponding nitro derivatives does not involve the oxoammonium ion, as reported previously. The mechanistic proposals are supported mainly by ESR investigation and electrochemical data. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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Section: Discussionsupporting

confidence: 75%

“…· NO 2 is not able to oxidize the nitrosobenzene by electron transfer, [33] while it may be trapped by the nitroso group through the oxygen atom, affording a spin adduct such as 13, which spontaneously gives the nitro derivative. [31] Unfortunately, in the case of 3a (A) all attempts to detect the signal of 13 failed.…”

Section: Discussionmentioning

confidence: 99%

On the Role of Nitrogen Monoxide (Nitric Oxide) in the Nitration of a Tyrosine Derivative and Model Compounds

Giorgini¹,

Petrucci

Astolfi³

et al. 2002

Eur. J. Org. Chem.

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“…The redox potentials of isopropanol/acetone and nitrobenzene/azoxybenzene, respectively, are ~0.1 and −0.8 V as referenced to the standard hydrogen electrode (SHE) 31 , 32 . Therefore, the photoexcited e − in the conduction band (CB) of g-C 3 N 4 is energetically favourable to initiate the nitrobenzene reduction, as depicted in Fig.…”

Section: Discussionmentioning

confidence: 99%

“…a Energy scheme of the photocatalytic nitrobenzene reduction on g-C 3 N 4 . The redox potentials of nitrobenzene (NB) to azoxybenzene plus isopropanol (IP) to acetone (AC), and the CB and VB positions are referenced to the SHE 32 , 33 . b and c suggested possible active sites for isopropanol oxidation and nitrobenzene reduction according to calculations.…”

Section: Discussionmentioning

confidence: 99%

Light-tuned selective photosynthesis of azo- and azoxy-aromatics using graphitic C3N4

Dai

Li²,

Shen³

et al. 2018

Nat Commun

168

144

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Solar-driven photocatalysis has attracted significant attention in water splitting, CO2 reduction and organic synthesis. The syntheses of valuable azo- and azoxyaromatic dyes via selective photoreduction of nitroaromatic compounds have been realised using supported plasmonic metal nanoparticles at elevated temperatures (≥90 °C); however, the high cost, low efficiency and poor selectivity of such catalyst systems at room temperature limit their application. Here we demonstrate that the inexpensive graphitic C3N4 is an efficient photocatalyst for selective syntheses of a series of azo- and azoxy-aromatic compounds from their corresponding nitroaromatics under either purple (410 nm) or blue light (450 nm) excitation. The high efficiency and high selectivity towards azo- and azoxy-aromatic compounds can be attributed to the weakly bound photogenerated surface adsorbed H-atoms and a favourable N-N coupling reaction. The results reveal financial and environmental potential of photocatalysis for mass production of valuable chemicals.

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“…The electrochemistry of nitrosoarenes had been extensively studied by CV in aprotic solvents, such as MeCN, DMF or DMSO, [24–26] primarily as a result of their participation as an intermediate during the reduction of nitroaromatic reduction, together with their application as spin traps. Aromatic C‐ nitroso compounds are known to exist as free monomers in equilibrium with cis ‐ or trans ‐ azodioxy (−( − O)N + = + N(O − )−) dimers in solution, with consequences for their electrochemical behaviour.…”

Section: Introductionmentioning

confidence: 99%

Decorating BODIPY with Electron‐Withdrawing NO Group: Spectroelectrochemical Consequences and Computational Investigation

et al. 2021

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4,4‐difluoro‐5,7‐dimethyl‐4‐bora‐3a,4a‐diaza‐s‐indacene (BODIPY) and derivatives are an outstanding class of fluorescent dyes. Herein, we report on the introduction of a nitrosyl moiety into the BODIPY structure and its dramatic effect on the observed electrochemical reaction mechanism. 6‐Nitrosyl‐8‐phenyl‐BODIPY and its 5‐nitrosyl positional isomer, compounds 2 and 3, respectively, were obtained from the meso precursor, 8‐phenyl‐BODIPY (1), by nitrosation. Electrochemical studies for 1–3 are reported. Cyclic voltammetry and differential pulse voltammetry in degassed DMF or in MeCN (reduction+oxidation), both with n‐Bu4NPF6 (0.1 mol L−1), were obtained. Compound 1 displays the usual behaviour for 8‐phenyl substituted BODIPYs. The addition of the acceptor nitroso group in compounds 2 (in position β) and 3 (in position α), leads to a different profile. For all the compounds, the nitroso group greatly facilitates the reductions. For compound 3 (EpIc=−0.238 V), the first to be reduced is the nitroso group, due to the stability of the electrogenerated radical anion, along with non‐bonding interactions with the electronegative boron difluoride. This is different from compound 2 (EpIc=−0.351 V) with a β‐nitroso group, where the nitroso‐based facilitated reduction occurs in the substituted BODIPY core. Spectroelectrochemistry coupled with analysis through conceptual density functional theory (CDFT) corroborate the voltammetric results and explain the unexpected reactivity differences.

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Spin trapping in electrochemistry. Nonaqueous electrochemical behavior of nitroso spin traps

Cited by 31 publications

References 0 publications

On the Role of Nitrogen Monoxide (Nitric Oxide) in the Nitration of a Tyrosine Derivative and Model Compounds

On the Role of Nitrogen Monoxide (Nitric Oxide) in the Nitration of a Tyrosine Derivative and Model Compounds

Light-tuned selective photosynthesis of azo- and azoxy-aromatics using graphitic C3N4

Decorating BODIPY with Electron‐Withdrawing NO Group: Spectroelectrochemical Consequences and Computational Investigation

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