Electrochemical and computational study of the initiation step in the photoinduced electron transfer reaction between sulphur and selenide nucleophiles toward 1‐bromonaphthalene

Bouchet, Lydia M.; Pierini, Adriana B.; Brunetti, Verónica; Argüello, Juan E.

doi:10.1002/poc.3568

Cited by 4 publications

(6 citation statements)

References 33 publications

(30 reference statements)

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“…According to previous results and considering only the overall product yield distribution, thiobenzamide, thiourea, thioacetamide, ,, selenobenzamide, selenourea, and selenocyanate anions have similar reactivities toward 1-naphthyl radical, which is formed by photoinduced electron transfer followed by C–Br fragmentation (eq ). Considering that the S RN 1 reaction comprises initiation, propagation, and termination steps, it is of interest to evaluate the relative reactivity of the different sulfur and selenium anions toward 1-naphthyl radical in competitive experiments.…”

Section: Resultsmentioning

confidence: 80%

“…This difference can be explained considering that the overall reactivity comprises both initiation and propagation steps, where the lower efficiency of the selenium anions lies on a poor electron donor capacity (initiation step) and/or shorter propagation chain. 18 To get a deeper insight into the reaction mechanism and molecular properties that account for the different addition efficiencies of anions 1−5 and selenoacetamide anion (7) against 1-naphthyl radical, a topographic exploration of the potential energy surface for the radical nucleophilic coupling reaction was modeled.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The latter is evidenced by the fact that sulfur derivatives give similar yields at shorter reaction times. This difference can be explained considering that the overall reactivity comprises both initiation and propagation steps, where the lower efficiency of the selenium anions lies on a poor electron donor capacity (initiation step) and/or shorter propagation chain …”

Section: Resultsmentioning

confidence: 99%

“…Our first contribution to the chalcogenide chemistry overcomes this drawback by the use of sulfur-centered nucleophiles such as thiourea, thioacetate, thiobenzamide, and thioacetamide anions for the synthesis of aryl sulfide anions (ArS – ) and several sulfur aromatic compounds from moderate to good yields. Later on, this methodology was extended to selenium using selenourea, selenobenzamide, and selenocyanate ions in photoinduced S RN 1 reactions as a “one-pot” method to obtain aryl selenide anions among other examples, including a number of selenoethers .…”

Section: Introductionmentioning

confidence: 99%

“…The synthetic relevance of our reaction protocol for the chalcogenide installation in aromatic rings has been established; − still, scarce information on the dynamic and direct comparison between sulfur and selenium analogues is lacking. Therefore, the aim of the present work is to study the reactivity of sulfur- and selenium-centered nucleophiles, like – SC(NH)C 6 H 5 ( 1 ), – SC(NH)NH 2 ( 2 ), – SC(NH)CH 3 ( 3 ), – SeC(NH)C 6 H 5 ( 4 ), – SeC(NH)NH 2 ( 5 ), – SeCN ( 6 ), and – SeC(NH)CH 3 ( 7 ), toward 1-naphthyl radicals, as a model reaction.…”

Section: Introductionmentioning

confidence: 99%

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Combined Experimental and Theoretical Studies on the Radical Nucleophile Addition Reaction for Sulfide- and Selenide-Centered Anions

et al. 2019

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The reactivity of sulfur- and selenium-centered nucleophiles toward 1-naphthyl radicals was studied in dimethylsulfoxide. The photostimulated reaction of sulfide anions, –SC(NH)C6H5 (1), –SC(NH)NH2 (2), and –SC(NH)CH3 (3), renders, after the addition of MeI, methyl 1-naphthylsulfide as a main product together with bis(1-naphthyl) sulfide and naphthalene under irradiation. Concordantly, the reaction of selenide anions, –SeC(NH)C6H5 (4), –SeC(NH)NH2 (5), and –SeCN (6), produces methyl 1-naphthyl selenide, bis(1-naphthyl) selenide, and naphthalene in the presence of potassium tert-butoxide anion (entrainment conditions). Absolute rate constants for the coupling of ions 1–6 to 1-naphthyl radicals were determined; as a general trend, the selenide-centered nucleophiles enhance in 2 times the reactivity of their sulfide analogues. From the mechanistic study, it is proposed that the unstable radical anion produced by the addition of the nucleophile to 1-naphthyl radical affords, after fragmentation, 1-naphthylsulfide/selenide anion. In addition, experimental results are discussed in terms of density functional theory calculations. There is a generally good agreement between the experimental and the calculated reactivities, the spin density being the main parameter to describe the difference found among the anions under study. Moreover, the calculations predict that anion –SeC(NH)CH3 (7) would be a good candidate for the synthesis of selenide derivatives.

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Section: Resultsmentioning

confidence: 80%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Combined Experimental and Theoretical Studies on the Radical Nucleophile Addition Reaction for Sulfide- and Selenide-Centered Anions

et al. 2019

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Sulfur Radicals and Their Application

Glass

2018

Top Curr Chem (Z)

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The present review highlights recent developments in the chemistry of sulfur radicals. Background material essential to the understanding of these developments is briefly reviewed and references to previous in depth reviews are cited. The exciting applications of current research involving sulfur radicals in bonding theory, organic synthesis, polymer chemistry, materials science, and biochemistry are outlined.

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Photoinduced One-Electron Oxidation of Aromatic Selenides: Effect of the Structure on the Reversible Dimerization Reaction

Bouchet

Argüello

2018

J. Org. Chem.

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The photochemical one-electron oxidation of alkyl aryl selenides was studied by means of laser flash photolysis (355 nm). Quenching of the sensitizers in their excited state leads to selenide radical cation in the presence of selenium derivatives. The π-type dimer of methyl phenyl selenide radical cation was detected at 630 nm at expenses of the monomeric radical cation (530 nm). The effect of modification of the aryl and alkyl substituents was also studied, resulting that the formation of dimers depends on both, the electronic properties and steric hindrance of the substituents. Both effects, an increase in steric hindrance in the alkyl moiety or the presence of strongly electron donor groups in the aromatic substituent that stabilizes the radical cation, prevent the dimer formation.

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Electrochemical and computational study of the initiation step in the photoinduced electron transfer reaction between sulphur and selenide nucleophiles toward 1‐bromonaphthalene

Cited by 4 publications

References 33 publications

Combined Experimental and Theoretical Studies on the Radical Nucleophile Addition Reaction for Sulfide- and Selenide-Centered Anions

Combined Experimental and Theoretical Studies on the Radical Nucleophile Addition Reaction for Sulfide- and Selenide-Centered Anions

Sulfur Radicals and Their Application

Photoinduced One-Electron Oxidation of Aromatic Selenides: Effect of the Structure on the Reversible Dimerization Reaction

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