Caged Nitric Oxide–Thiyl Radical Pairs

Wu, Zhuang; Chen, Changyun; Liu, Jie; Lu, Y.; Xu, Jian; Li, Xiangyang; Cui, Ganglong; Trabelsi, Tarek; Francisco, Joseph S.; Mardyukov, Artur; Eckhardt, André K.; Schreiner, Peter R.; Zeng, Xiaoqing

doi:10.1021/jacs.8b12746

Cited by 17 publications

(15 citation statements)

References 60 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The barrier height is reduced to merely 0.16 ± 0.03 kcal mol –1 when running the kinetics under the continuous irradiation from the IR globar. The capture of •OH···OS in the photochemistry of HOSO• resembles the caged nitric oxide–thiyl radical pairs (RS•···•ON) formed in the photochemistry of S -nitrosothiols (RSNO, R = Me and Et) …”

mentioning

confidence: 99%

Capture of the Sulfur Monoxide–Hydroxyl Radical Complex

et al. 2020

Self Cite

View full text Add to dashboard Cite

The elusive hydrogen-bonded sulfur monoxide–hydroxyl radical complex (•OH···OS), a missing intermediate in the atmospheric chemistry of SO2, was generated in the 266 nm laser photolysis of the sulfinyl radical HOSO• in cryogenic Ar-matrixes. In addition to the IR spectroscopic characterization with deuteration, its thermal conversion to HOSO• with an activation barrier of 0.33 ± 0.11 kcal mol–1 (calcd 0.32 kcal mol–1, CCSD(T)-F12a/AVTZ) in the temperature range of 15.0–21.0 K and a H/D kinetic isotope effect of 2.4 at 16.0 K have been observed.

show abstract

mentioning

confidence: 99%

Capture of the Sulfur Monoxide–Hydroxyl Radical Complex

et al. 2020

Self Cite

View full text Add to dashboard Cite

show abstract

“…2a) isolated in N 2 -matrix at 10 K shows the formation of CH 3 S• (2, 1398.3, 1053.4, and 783.0 cm −1 , Fig. 2b) 39 , •CH 3 (3, 611.1 cm −1 ) 47 , and •NO (4, 1874.9 cm −1 ) 46 . Owing to the moderate BDEs for C-S (70 kcal mol −1 ) and C-H (49 kcal mol −1 ) bonds in 2 38 , further increase of the pyrolysis temperature to ca.…”

Section: Resultsmentioning

confidence: 93%

“…Sample preparation. S-Nitrosothiol (CH 3 SNO) was prepared by reacting CH 3 SH with ClNO according to the published protocol 46 . Ar (≥99.999%, Messer), N 2 (≥99.999%, Messer), O 2 (≥99.999%, Messer), 15 N 2 (98 atom %, Aldrich), 18 O 2 (97 atom %, Aldrich) gases were used without further purification.…”

Section: Methodsmentioning

confidence: 99%

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

Shao

Zhu

et al. 2022

Commun Chem

Self Cite

View full text Add to dashboard Cite

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.

show abstract

“…Complex 8 is stabilized by 59 kcal mol À1 relative to bisected isomer 7c.C ombinationo ft he two radicals to give syn-nitritoborane 9b is strongly exothermic and its barrierc an likelyb eo vercome by due to the energy gained by formation andt he fixation in am atrix cage. [51] A very low barrier (0.2 kcal mol À1 )N ÀOb ond rotation finally gives the more stable and experimentally observed anti-nitritoborane 9a.…”

Section: Computationals Tudiesmentioning

confidence: 93%

Unusual Nitrene Oxidation Product Formation by Metathesis Involving the Dioxygen O−O and Borylnitrene B−N Bonds

Bhagat

Schumann

Bettinger

2020

Chemistry A European J

View full text Add to dashboard Cite

The reactiono fd ioxygen with nitrenes can have significant energy barriers, although both reactants are triplet diradicals and the formationof nitroso-O-oxides is spin-allowed.B ym eans of matrix-isolation infrared spectroscopy in solid argon, nitrogen, and neon,a nd through high-level computational quantum chemistry,i ti ss hownh erein that a 3-nitreno-1,3,2-benzodioxaborole CatBN (Cat = catecholato) reacts with dioxygenu nder cryogenicc onditions thermally at temperatures as low as 7K to produce two distinct products, an anti-nitroso-O-oxide and an itritoborane CatBONO. The computedb arriers for the formation of nitroso-O-oxide isomersa re very low.W hereas anti-nitroso-O-oxide is kinetically trapped,i ts bisected isomer has av ery low barrierf or metathesis, yieldingt he CatBO + NO radicals in as trongly exothermic reaction; these radicals can combineu nder matrix-isolation conditions to give nitritoborane CatBONO. The trapped isomer, anti-nitroso-O-oxide, can form the nitri-toboraneC atBONO only after photoexcitation, possibly involvingi somerization to the bisectedi somer of anti-nitroso-O-oxide.

show abstract

Caged Nitric Oxide–Thiyl Radical Pairs

Cited by 17 publications

References 60 publications

Capture of the Sulfur Monoxide–Hydroxyl Radical Complex

Capture of the Sulfur Monoxide–Hydroxyl Radical Complex

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

Unusual Nitrene Oxidation Product Formation by Metathesis Involving the Dioxygen O−O and Borylnitrene B−N Bonds

Contact Info

Product

Resources

About