Electrochemically generated free radicals

Il'yasov, A. V.; Kargin, Yu. M.; Levin, Ya. A.; Morozova, I. D.; Mel'nikov, B. V.; Vafina, A. A.; Sotnikova, N.; Galeev, V. S.

doi:10.1007/bf00853900

Cited by 4 publications

(3 citation statements)

References 7 publications

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“…As to demonstrate the stabilizing effect of the spiro-fluorenyl tethers in 1 towards one-electron reduction we conducted EPR measurements of the radical anions of Ph 3 PO, which was obtained following the procedure for the preparation of 1 • . In contrast of observations of Evans et al, [17] the EPR spectrum of the chemical reduction of Ph 3 PO with potassium shows two radical species with only poorly resolved hyperfine splitting to the protons and hyperfine coupling constants A( 31 P) of 25.9 MHz (0.93 mT) and 59.9 MHz (2.14 mT), [18] which are smaller than that observed for 1 • withA( 31 P) of 99.9 MHz (3.57 mT), likely due to the interaction of the alkali cation with the Ph 3 PO derived radicals at RT (Fig S31). On the basis of our results the radical species could not be assigned to a specific structure, however, in both cases, less spin density is on the internal phosphorus atom, which is in agreement with the considerably smaller hyperfine coupling with the internal 31 P atom (I = 1/2, 100%) expected for the radical anion of Ph 3 PO A( 31 P) of 25.9 MHz (0.93 mT) and some decomposition product resulting from phenyl ring cleavage A( 31 P) of 59.9…”

Section: Electron Paramagnetic Resonance Measurementscontrasting

confidence: 71%

A Stable Crystalline Triarylphosphine Oxide Radical Anion

et al. 2016

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Triarylphosphine oxides (Ar P=O) are being intensely studied as electron-accepting (n-type) materials. Despite the widespread application of these compounds as electron conductors, experimental data regarding the structural and electronic properties of their negatively charged states remain scarce owing to their propensity for follow-up chemistry. Herein, a carefully designed triarylphosphine oxide scaffold is disclosed that comprises sterically demanding spirofluorenyl moieties to shield the central phosphoryl (P=O) moiety. This compound undergoes chemical one-electron reduction to afford an exceptionally stable radical anion, which was isolated and characterized by X-ray crystallography for the very first time. The experimental data, corroborated by computational studies, shall allow for the construction of phosphine oxide materials with enhanced stability.

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Section: Electron Paramagnetic Resonance Measurementscontrasting

confidence: 71%

A Stable Crystalline Triarylphosphine Oxide Radical Anion

et al. 2016

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“…The reaction mechanism can therefore be described as the following combination of reactions from Table I: (1) + (2) + a(4) + (! -«) [(7) (or 9) + 0(11) + (1 -01 (15)(16)(17)(18)], leading to the balance equation…”

Section: Resultsmentioning

confidence: 99%

Electrochemical reduction of phosphonium cations in media of low proton availability

Savéant¹,

Binh²

1977

J. Org. Chem.

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The electrochemical reduction of a series of alkyltriphenylphosphonium cations is studied in media of low proton availability as a function of the alkyl group, initial concentration, nature and water content of the solvent, and electrolysis potential. With reference to previous work on Ph4P+ and on phosphoniums giving rise to stable ylides, a general pict ure of the mechanisms is drawn with emphasis on the following points: (1) interference of the starting cation as an acid in the reaction process leading to ylide or phosphine oxide formation and to Hofmann degradation;(2) competition between the two-electron pathway involving the above-mentioned reactions and the one-electron pathway leading to dimerization and/or disproportionation of the initially expelled radical; (3) factors determining the competition between the one-electron and the two-electron pathway and the various reactions inside each of them; (4) orientation of cleavage in electrochemical reduction and phosphine oxide formation.

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“…Several organophosphorus anion radicals such as Ph3P•were generated polarographically for ESR studies (494,495). Chemical cleavage rates and reduction data were correlated for p-RCeH4C0P(0)(0Et)2 at pH 5 to 8 (538).…”

Section: Sulfur Compoundsmentioning

confidence: 99%

Organic polarography

Pietrzyk¹

1974

Anal. Chem.

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Chemical Titles, and readily available journals ending November 30, 1973. This period has seen a continued growth in the use of polarography and related electrochemical techniques to follow chemical reactions and to supplement other physical and spectral measurements for purposes of characterization. Interest in applications toward biochemical and pharmaceutical problems has also increased. There also appears to be renewed interest in utilizing polarographic and related electrochemical data to predict and follow organoelectrochemical synthesis.In this review the symbols cv, dc, ac, and op are used to identify cyclic voltammetry, direct current polarography, alternating current polarography, and oscillographic polarography, respectively. Also, no attempt was made to list all organic polarographic references.

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Electrochemically generated free radicals

Cited by 4 publications

References 7 publications

A Stable Crystalline Triarylphosphine Oxide Radical Anion

A Stable Crystalline Triarylphosphine Oxide Radical Anion

Electrochemical reduction of phosphonium cations in media of low proton availability

Organic polarography

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