Die SF5Ox‐Radikale, x=0–3

Kronberg, Marc; Ahsen, Stefan von; Willner, Helge; Francisco, Joseph S.

doi:10.1002/ange.200461235

Cited by 6 publications

(4 citation statements)

References 28 publications

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“…In experiments with equilibrated 16/18 O 2 mixtures, each of these two bands split into three components, located at 1543.8, 1501.5, and 1458.2 cm −1 (Figure 1, lower trace), and 3063.4, 2981.6, and 2896.2 cm −1 , respectively. At first glance, this 16/18 O isotopic pattern points to equivalent bound oxygen atoms of the O 2 unit, which is in contrast to the bonding found in the chainlike trioxy radicals XOOO (XO=F 3 CO,2 F 5 SO,3 and ClO 4 4). However, the observed 16/18 O isotopic pattern for the OO stretch in FSO 3 /O 2 is very similar to that found for FOO11 and more recently for the terminal OO stretch in F 3 COOO 12.…”

Section: Calculated Ir Data For Two Isomers Of Fso3/o2 Experimental mentioning

confidence: 83%

“…The short lifetime prevented further spectroscopic investigations. Previously we studied in noble gas matrices O 2 complexes of several oxy radicals such as CF 3 O/O 2 ,2 SF 5 O/O 2 ,3 and ClO 4 /O 2 4. However, dioxygen complexes of polyoxy radicals such as FSO 3 have not yet sufficiently been characterized.…”

Section: Calculated Ir Data For Two Isomers Of Fso3/o2 Experimental mentioning

confidence: 99%

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Side‐On versus End‐On Bonding of O₂ to the FSO₃ Radical: Matrix Isolation and Ab Initio Study of FSO₅

et al. 2007

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Dedicated to Professor Friedhelm Aubke on the occasion of his 75th birthdayOxy radicals of non-metals such as nitrogen, chlorine, or sulfur play an important part in atmospheric chemistry. They generally form weak complexes with dioxygen. A recent study [1] on the kinetics of formation and the decomposition of the FSO 3 /O 2 complex attracted our interest. The intermediate formed by laser flash photolysis (l = 193 nm) of FSO 2 OF in the presence of O 2 features a strong visible absorption at 450 nm and was claimed to be the chainlike trioxy radical FSO 2 OOO.[1] The oxygenated radical was found to dissociate unimolecularly on a millisecond timescale to yield FSO 3 + O 2 .[1] The short lifetime prevented further spectroscopic investigations. Previously we studied in noble gas matrices O 2 complexes of several oxy radicals such as CF 3 O/O 2 , [2] SF 5 O/O 2 , [3] and ClO 4 /O 2 .[4] However, dioxygen complexes of polyoxy radicals such as FSO 3 have not yet sufficiently been characterized. Herein we report the matrix isolation and a combined UV/Vis/infrared spectroscopic and quantum-chemical characterization of the FSO 3 /O 2 complex. The infrared spectra of the precursor for the synthesis of FSO 3 , the peroxide FSO 2 OOSO 2 F (S 2 O 6 F 2 ), [5,6] isolated in solid argon at 14 K or in neon at 6 K, revealed no impurities, but did show splitting of the bands owing to the presence of several rotamers. Increasing the temperature of the spray-on nozzle during matrix deposition changed the relative intensities of these splittings, and bands associated with the FSO 3 radical, [7] formed by thermal dissociation of S 2 O 6 F 2 according to Equation (1), appear in the IR matrix spectra.S 2 O 6 F 2 is almost completely dissociated at a pyrolysis temperature of 160 8C, as demonstrated in Figure 1 (upper trace). In contrast to previous matrix experiments, [7] much weaker bands of HSO 3 F, H 2 O, CO 2 , HF, and S 2 O 5 F 2 are found in the spectra.The thermolysis products of S 2 O 6 F 2 were trapped in a Ne matrix containing 10 % of O 2 to investigate the reaction of FSO 3 radicals with molecular oxygen. Part of the IR spectrum of this experiment is displayed in Figure 1 (middle trace). It reveals a strong decrease in intensity of all bands attributed to FSO 3 and the appearance of new broad IR bands of the

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Section: Calculated Ir Data For Two Isomers Of Fso3/o2 Experimental mentioning

confidence: 83%

Section: Calculated Ir Data For Two Isomers Of Fso3/o2 Experimental mentioning

confidence: 99%

Side‐On versus End‐On Bonding of O₂ to the FSO₃ Radical: Matrix Isolation and Ab Initio Study of FSO₅

et al. 2007

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“…Wir haben bereits O 2 ‐Komplexe von Oxy‐Radikalen, z. B. CF 3 O/O 2 ,2 SF 5 O/O 2 3 und ClO 4 /O 2 ,4 in Edelgasmatrices untersucht; Disauerstoff‐Komplexe von Polyoxy‐Radikalen wie FSO 3 sind bisher allerdings noch nicht ausreichend charakterisiert worden. Hier berichten wir über die Matrixisolation sowie über eine kombinierte UV/Vis/Infrarot‐spektroskopische und quantenmechanische Charakterisierung des FSO 3 /O 2 ‐Komplexes.…”

Section: Berechnete Ir‐daten Für Zwei Isomere Von Fso3/o2 Experimentunclassified

“…3063.4, 2981.6 und 2896.2 cm −1 liegen. Auf den ersten Blick weist dieses 16/18 O‐Isotopenmuster auf äquivalent gebundene Sauerstoffatome der O 2 ‐Einheit hin, sodass eine End‐on‐O 2 ‐Koordination, analog zu der in den linearen Trioxy‐Radikalen XOOO (XO=F 3 CO,2 F 5 SO3 und ClO 4 4), zunächst ausgeschlossen wurde. Es zeigt sich jedoch, dass die 16/18 O‐Isotopenmuster der O 2 ‐Einheiten von FOO11 und dem erst kürzlich untersuchten F 3 COOO12, 13 sehr ähnlich zu dem von FSO 3 /O 2 sind.…”

Section: Berechnete Ir‐daten Für Zwei Isomere Von Fso3/o2 Experimentunclassified

Side‐on‐ oder End‐on‐Koordination von O₂ am FSO₃‐Radikal: Matrixisolation und Ab‐initio‐Untersuchung von FSO₅

et al. 2007

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Das Methylsulfonyloxyl‐Radikal, CH₃SO₃

et al. 2015

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Die SF₅O_x‐Radikale, x=0–3

Abstract: O für O: Die Radikale SF5Ox (x=0–3; siehe Bild) wurden in Matrix isoliert und durch IR‐ und UV‐Spektroskopie, Photolyseexperimente und quantenchemische Rechnungen charakterisiert. Ihre mögliche Beteiligung an Reaktionen in der Atmosphäre wird diskutiert.

Cited by 6 publications

References 28 publications

Side‐On versus End‐On Bonding of O₂ to the FSO₃ Radical: Matrix Isolation and Ab Initio Study of FSO₅

Side‐On versus End‐On Bonding of O₂ to the FSO₃ Radical: Matrix Isolation and Ab Initio Study of FSO₅

Side‐on‐ oder End‐on‐Koordination von O₂ am FSO₃‐Radikal: Matrixisolation und Ab‐initio‐Untersuchung von FSO₅

Das Methylsulfonyloxyl‐Radikal, CH₃SO₃

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Die SF5Ox‐Radikale, x=0–3

Abstract: O für O: Die Radikale SF5Ox (x=0–3; siehe Bild) wurden in Matrix isoliert und durch IR‐ und UV‐Spektroskopie, Photolyseexperimente und quantenchemische Rechnungen charakterisiert. Ihre mögliche Beteiligung an Reaktionen in der Atmosphäre wird diskutiert.

Cited by 6 publications

References 28 publications

Side‐On versus End‐On Bonding of O2 to the FSO3 Radical: Matrix Isolation and Ab Initio Study of FSO5

Side‐On versus End‐On Bonding of O2 to the FSO3 Radical: Matrix Isolation and Ab Initio Study of FSO5

Side‐on‐ oder End‐on‐Koordination von O2 am FSO3‐Radikal: Matrixisolation und Ab‐initio‐Untersuchung von FSO5

Das Methylsulfonyloxyl‐Radikal, CH3SO3

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Die SF₅O_x‐Radikale, x=0–3

Side‐On versus End‐On Bonding of O₂ to the FSO₃ Radical: Matrix Isolation and Ab Initio Study of FSO₅

Side‐On versus End‐On Bonding of O₂ to the FSO₃ Radical: Matrix Isolation and Ab Initio Study of FSO₅

Side‐on‐ oder End‐on‐Koordination von O₂ am FSO₃‐Radikal: Matrixisolation und Ab‐initio‐Untersuchung von FSO₅

Das Methylsulfonyloxyl‐Radikal, CH₃SO₃