Generation and characterization of the phenylthiyl radical and its oxidation to the phenylthiylperoxy and phenylsulfonyl radicals

Mardyukov, Artur; Schreiner, Peter R.

doi:10.1039/c6cp04278c

Cited by 16 publications

(24 citation statements)

References 59 publications

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“…Natural population analyses of the spin densities in the phenyl-substituted sulfur-centered radicals PhSO x • (x = 0−2) were computed at the B3LYP/def2-TZVPP level (Figure 7). In accord with the recent computations for PhS• and PhSO 2 •, 11 the densities for the unpaired electron spin in all these species…”

Section: ■ Introductionsupporting

confidence: 88%

“…65 The absence of the IR bands for the O 2 -trapping product of PhSO• (3) or derivatives suggests that no photooxidation happens. Instead, PhSO• (3) prefers isomerization to PhOS• (4), and the latter combines O 2 in the same matrix cages to furnish PhOSOO• with immediate photofragmentation to PhO• (11) and open-chain SOO, and the last species isomerizes to SO 2 under the irradiation conditions (Figures S2−S3). 69 Quantum Chemical Computations.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Sulfur-containing radicals like thiyl radicals R-S•, − sulfinyl radicals R-SO•, − sulfonyl radicals R-SO 2 •, − and sulfonyloxyl radicals R-SO 3 • − are highly relevant to atmospheric chemistry, biology, and organic synthesis. For instance, simple sulfinyl radicals HSO• and CH 3 SO• , form as fleeting intermediates in the oxidation of volatile organic sulfur compounds (VOSCs) in the atmosphere.…”

Section: Introductionmentioning

confidence: 99%

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Phenylsulfinyl Radical: Gas-Phase Generation, Photoisomerization, and Oxidation

Wan

et al. 2018

J. Am. Chem. Soc.

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Arylsulfinyl radicals are key intermediates in sulfoxide chemistry. The parent molecule, phenylsulfinyl radical PhSO•, has been generated for the first time in the gas phase through high-vacuum flash pyrolysis of PhS(O)R (R = CF and Cl) at about 1000 K. Upon UV light irradiation (365 nm), PhSO• isomerizes to novel oxathiyl radical PhOS• in cryogenic matrices (2.8 K). Prolonged irradiation causes further isomerization of PhOS• to 2-hydroxyphenylthiyl radical, the formation of which has been also observed in the 193 nm laser photolysis of matrix-isolated 2-hydroxybenzenethiol. Concomitantly, ring-opening occurs during the UV photolysis of PhOS• and 2-hydroxybenzenethiol and forms an acyclic thioketoketene radical. Phenylsulfinyl radical reacts partially with molecular oxygen in the gas phase and yields phenyl radical Ph• and OSOO. Upon irradiation (365 nm), the isomeric oxathiyl radical also combines O with immediate dissociation to phenoxy radical PhO• and SO. The identification of the intermediates with IR and UV-vis spectroscopy is supported by quantum chemical computations at the B3LYP/def2-TZVPP and UCCSD(T)/aug-cc-pV(D+d)Z levels of theory. The isomerization of PhSO• has been discussed based on the computed potential energy profile and the comparison with the intensively explored photochemistry of phenylperoxy radical PhOO•.

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Section: ■ Introductionsupporting

confidence: 88%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Phenylsulfinyl Radical: Gas-Phase Generation, Photoisomerization, and Oxidation

Wan

et al. 2018

J. Am. Chem. Soc.

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“…4). The frequency is close to the ν(OO) mode in other peroxyl radicals such as PhSOO• (1173 cm −1 ) 52 and CH 3 S(O)OO• (syn/anti: 1100.3/1081.3 cm −1 ) 23 with comparable 16/18 O-isotopic shifts of 64 and 61.0/58.3 cm −1 , respectively. The bands at 547.6 and 443.7 cm −1 correspond to the S-O stretching (calc.…”

Section: Resultssupporting

confidence: 57%

“…The resulting IR difference spectrum shows exclusive depletion of 11 (Fig. 3b), and sulfonyl radical CH (→ PhSO 2 •) 52 and OSOO (→ SO 3 ) 53 . The previously 28 proposed secondary oxidation of 11 with O 2 to form CH 3 SO• in the gas phase was not observed under the matrix-isolation conditions.…”

Section: Resultsmentioning

confidence: 99%

Spectroscopic characterization of two peroxyl radicals during the O2-oxidation of the methylthio radical

Shao

Zhu

et al. 2022

Commun Chem

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The atmospheric oxidation of dimethyl sulfide (DMS) yields sulfuric acid and methane sulfonic acid (MSA), which are key precursors to new particles formed via homogeneous nucleation and further cluster growth in air masses. Comprehensive experimental and theoretical studies have suggested that the oxidation of DMS involves the formation of the methylthio radical (CH3S•), followed by its O2-oxidation reaction via the intermediacy of free radicals CH3SOx• (x = 1–4). Therefore, capturing these transient radicals and disclosing their reactivity are of vital importance in understanding the complex mechanism. Here, we report an optimized method for efficient gas-phase generation of CH3S• through flash pyrolysis of S-nitrosothiol CH3SNO, enabling us to study the O2-oxidation of CH3S• by combining matrix-isolation spectroscopy (IR and UV–vis) with quantum chemical computations at the CCSD(T)/aug-cc-pV(X + d)Z (X = D and T) level of theory. As the key intermediate for the initial oxidation of CH3S•, the peroxyl radical CH3SOO• forms by reacting with O2. Upon irradiation at 830 nm, CH3SOO• undergoes isomerization to the sulfonyl radical CH3SO2• in cryogenic matrixes (Ar, Ne, and N2), and the latter can further combine with O2 to yield another peroxyl radical CH3S(O)2OO• upon further irradiation at 440 nm. Subsequent UV-light irradiation (266 nm) causes dissociation of CH3S(O)2OO• to CH3SO2•, CH2O, SO2, and SO3. The IR spectroscopic identification of the two peroxyl radicals CH3SOO• and CH3S(O)2OO• is also supported by 18O- and 13C-isotope labeling experiments.

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Photochemistry of 2-Iodobenzothiazole and Iodine-Triggered 2-Isocyanophenylthiyl Radical Cyclization in Argon Matrices

et al. 2023

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The photochemistry of 2-iodobenzothiazole (IBT) was investigated in an argon matrix at 4 K. Irradiating matrix-isolated IBT at λ = 254 nm led to the formation of 2-isocyanophenylthiyl radical 3 and benzothiirene 4; surprisingly, the 2-dehydrobenzothiazole radical 1 was not detected. A subsequent 365 nm irradiation or annealing of matrix containing 3 and iodine atom (at 30 K) reverted the precursor IBT, indicating an iodinetriggered thiyl radical-based cyclization, which was confirmed by computations using density functional theory. For gaining mechanistic insights, similar investigations were performed using benzothiazole BT as a precursor. Once again, the 254 nm light-induced C−S scission accompanied by H-shift led to 2-isocyanothiophenol 7. A conformational analysis of 2-isocyanothiophenol 7 and its photochemistry was also carried out with the help of IR spectroscopy under cryogenic conditions and computations. Considering the importance of thiyl radicals in biomolecular pathways, the investigations on its photochemical generation and a rare, reversible phenomenon of iodine-mediated cyclization under cryogenic conditions are insightful for fundamental photochemistry and sulfur chemistry.

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Generation and characterization of the phenylthiyl radical and its oxidation to the phenylthiylperoxy and phenylsulfonyl radicals

Cited by 16 publications

References 59 publications

Phenylsulfinyl Radical: Gas-Phase Generation, Photoisomerization, and Oxidation

Phenylsulfinyl Radical: Gas-Phase Generation, Photoisomerization, and Oxidation

Spectroscopic characterization of two peroxyl radicals during the O2-oxidation of the methylthio radical

Photochemistry of 2-Iodobenzothiazole and Iodine-Triggered 2-Isocyanophenylthiyl Radical Cyclization in Argon Matrices

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