Observation of chlorine oxide (ClO3) radical in aqueous chlorate solution by pulse radiolysis

Domae, Masafumi; Katsumara, Yosuke; Jiang, Pei Yun; Nagaishi, Ryuji; Hasegawa, Chisato; Ishigure, Kenkichi; Yoshida, Yasuhiko

doi:10.1021/j100052a031

Cited by 19 publications

(20 citation statements)

References 3 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…An identical EPR spectrum can be obtained from KClO 3 in CDCl 3 (Figure S12). These observations are consistent with the presence of a trace quantity of chlorate that was not removed despite extensive washing; UV irradiation of chlorate has been reported to promote a variety of radical-generating processes . Dissolution of the sample of 1 prepared by Method B in HNO 3 and analysis by ICP-MS indicated the presence of K + .…”

Section: Resultssupporting

confidence: 81%

“…These observations are consistent with the presence of a trace quantity of chlorate that was not removed despite extensive washing; UV irradiation of chlorate has been reported to promote a variety of radical-generating processes. 86 Dissolution of the sample of 1 prepared by Method B in HNO 3 and analysis by ICP-MS indicated the presence of K + . Chlorate is not detectable by IR analysis (Figure S13); however, negativemode ESI-MS of 1 prepared by Method B indicates the presence of ClO 3 − (m/z = 82.953 (exptl); 82.954 (calcd)) (Figure S14).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

See 1 more Smart Citation

Iodosylbenzene Coordination Chemistry Relevant to Metal–Organic Framework Catalysis

et al. 2019

View full text Add to dashboard Cite

Hypervalent iodine compounds formally feature expanded valence shells at iodine. These reagents are broadly used in synthetic chemistry due to the ability to participate in well-defined oxidation–reduction processes and because the ligand-exchange chemistry intrinsic to the hypervalent center allows hypervalent iodine compounds to be applied to a broad array of oxidative substrate functionalization reactions. We recently developed methods to generate these compounds from O2 that are predicated on diverting reactive intermediates of aldehyde autoxidation toward the oxidation of aryl iodides. Coupling the aerobic oxidation of aryl iodides with catalysts that effect C–H bond oxidation would provide a strategy to achieve aerobic C–H oxidation chemistry. In this Forum Article, we discuss the aspects of hypervalent iodine chemistry and bonding that render this class of reagents attractive lynchpins for aerobic oxidation chemistry. We then discuss the oxidation processes relevant to the aerobic preparation of 2-(tert-butylsulfonyl)iodosylbenzene, which is a popular hypervalent iodine reagent for use with porous metal–organic framework (MOF)-based catalysts because it displays significantly enhanced solubility as compared with unsubstituted iodosylbenzene. We demonstrate that popular synthetic methods to this reagent often provide material that displays unpredictable disproportionation behavior due to the presence of trace impurities. We provide a revised synthetic route that avoids impurities common in the reported methods and provides access to material that displays predictable stability. Finally, we describe the coordination chemistry of hypervalent iodine compounds with metal clusters relevant to MOF chemistry and discuss the potential implications of this coordination chemistry to catalysis in MOF scaffolds.

show abstract

Section: Resultssupporting

confidence: 81%

Section: ■ Results and Discussionmentioning

confidence: 99%

Iodosylbenzene Coordination Chemistry Relevant to Metal–Organic Framework Catalysis

et al. 2019

View full text Add to dashboard Cite

show abstract

“…Reaction of • OH Radicals in High Acidic Concentrations. In highly acidic solutions, the entire radiation energy would not be absorbed by water alone, and G ( • OH) would decrease with increasing concentration of HClO 4 as the radiolysis of HClO 4 does not produce • OH radicals . On the basis of the electron density variation between water and HClO 4 , the absorbance values are normalized with respect to G ( • OH).…”

Section: Resultsmentioning

confidence: 99%

Pulse Radiolysis Investigations on Acidic Aqueous Solutions of Benzene: Formation of Radical Cations

Mohan

Mittal

1998

J. Phys. Chem. A

View full text Add to dashboard Cite

The transient optical absorption bands (λ max ) 310, 350-500 nm, k ) 5.6 × 10 9 dm 3 mol -1 s -1 ) formed on pulse radiolysis of an acidic (HClO 4 ) 7.8 mol dm -3 ) aqueous solution of benzene are assigned to the solute radical cation formed on acid-catalyzed dehydration of the OH adduct. The solute radical cation is able to undergo an electron transfer reaction with Brwith a bimolecular rate constant of 8 × 10 9 dm 3 mol -1 s -1 . On the other hand, the OH adduct (λ max ) 310 nm) was oxidized by Fe(CN) 6 3with a bimolecular rate constant of 6.6 × 10 7 dm 3 mol -1 s -1 . The radical cation of benzene is a strong one-electron oxidant with oxidation potential in the range 2.1-2.4 V vs NHE.

show abstract

“…Finally the formation of ClO 3 was supported by the excellent agreement between observed and calculated ab initio IR band positions and intensities 2, 38–40, 115–119. In addition, time resolved UV spectra of pulse and γ ‐radiolysed or laser photolysed chlorate or perchloric acid solutions are assigned to ClO 3 or ClO 4 radicals, respectively 120–122…”

Section: Introductionmentioning

confidence: 58%

“…A critical evaluation of the literature data for other claims for the UV/Vis spectrum of ClO 3 96, 97, 120, 121, 140 leads to the conclusion that in all cases something else was observed, but not ClO 3 . In a recent study on laser photolysis of peroxydisulfate solutions containing chlorate, a very broad unsymmetrical band with a maximum at about 330 nm and a flat band at about 450 nm has been reported 122.…”

Section: Chlorine Trioxidementioning

confidence: 98%

The SAGES manual: fundamentals of laparoscopy, thoracoscopy, and GI endoscopy. 2nd Edn. C. E. H. Scott-Conner (ed.). 127 × 201 mm. Pp 840. Illustrated. 2006. Springer: Heidelberg. £38·50

Kazemier

2006

British Journal of Surgery

View full text Add to dashboard Cite

Observation of chlorine oxide (ClO3) radical in aqueous chlorate solution by pulse radiolysis

Cited by 19 publications

References 3 publications

Iodosylbenzene Coordination Chemistry Relevant to Metal–Organic Framework Catalysis

Iodosylbenzene Coordination Chemistry Relevant to Metal–Organic Framework Catalysis

Pulse Radiolysis Investigations on Acidic Aqueous Solutions of Benzene: Formation of Radical Cations

The SAGES manual: fundamentals of laparoscopy, thoracoscopy, and GI endoscopy. 2nd Edn. C. E. H. Scott-Conner (ed.). 127 × 201 mm. Pp 840. Illustrated. 2006. Springer: Heidelberg. £38·50

Contact Info

Product

Resources

About