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Article: Visible-Light Photocatalysis of C(sp3)-H Fluorination by the Uranyl Ion: Mechanistic Insights

TitleVisible-Light Photocatalysis of C(sp<sup>3</sup>)-H Fluorination by the Uranyl Ion: Mechanistic Insights
Authors
KeywordsC−H activation
ab initio calculations
single-electron transfer
uranium
photocatalysis
Issue Date2018
Citation
Angewandte Chemie - International Edition, 2018, v. 57, n. 36, p. 11812-11816 How to Cite?
Abstract© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim The uranyl dication shows photocatalytic activity towards C(sp3)−H bonds of aliphatic compounds, but not towards those of alkylbenzenes or cyclic ketones. Theoretical insights into the corresponding mechanisms are still limited. Multi-configurational ab initio calculations including relativistic effects reveal the inherent electron-transfer mechanism for the uranyl catalyzed C−H fluorination under blue light. Along the reaction path of the triplet state it was found that the hydrogen atom abstraction triggered by the electron-rich oxygen of the uranyl moiety is the rate-limiting step. The subsequent steps, that is, N−F and O−H bond breakage in a manner of concerted asynchronicity, generation of the targeted fluorinated product, and recovery of the photocatalyst are nearly barrierless. Moreover the single electron transfer between the reactive substrates plays a fundamental role during the whole photocatalytic cycle.
Persistent Identifierhttp://hdl.handle.net/10722/288749
ISSN
2019 Impact Factor: 12.959
2015 SCImago Journal Rankings: 6.229

 

DC FieldValueLanguage
dc.contributor.authorWu, Liangliang-
dc.contributor.authorCao, Xiaoyan-
dc.contributor.authorChen, Xuebo-
dc.contributor.authorFang, Weihai-
dc.contributor.authorDolg, Michael-
dc.date.accessioned2020-10-12T08:05:46Z-
dc.date.available2020-10-12T08:05:46Z-
dc.date.issued2018-
dc.identifier.citationAngewandte Chemie - International Edition, 2018, v. 57, n. 36, p. 11812-11816-
dc.identifier.issn1433-7851-
dc.identifier.urihttp://hdl.handle.net/10722/288749-
dc.description.abstract© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim The uranyl dication shows photocatalytic activity towards C(sp3)−H bonds of aliphatic compounds, but not towards those of alkylbenzenes or cyclic ketones. Theoretical insights into the corresponding mechanisms are still limited. Multi-configurational ab initio calculations including relativistic effects reveal the inherent electron-transfer mechanism for the uranyl catalyzed C−H fluorination under blue light. Along the reaction path of the triplet state it was found that the hydrogen atom abstraction triggered by the electron-rich oxygen of the uranyl moiety is the rate-limiting step. The subsequent steps, that is, N−F and O−H bond breakage in a manner of concerted asynchronicity, generation of the targeted fluorinated product, and recovery of the photocatalyst are nearly barrierless. Moreover the single electron transfer between the reactive substrates plays a fundamental role during the whole photocatalytic cycle.-
dc.languageeng-
dc.relation.ispartofAngewandte Chemie - International Edition-
dc.subjectC−H activation-
dc.subjectab initio calculations-
dc.subjectsingle-electron transfer-
dc.subjecturanium-
dc.subjectphotocatalysis-
dc.titleVisible-Light Photocatalysis of C(sp<sup>3</sup>)-H Fluorination by the Uranyl Ion: Mechanistic Insights-
dc.typeArticle-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/anie.201806554-
dc.identifier.pmid29984885-
dc.identifier.scopuseid_2-s2.0-85052452111-
dc.identifier.volume57-
dc.identifier.issue36-
dc.identifier.spage11812-
dc.identifier.epage11816-
dc.identifier.eissn1521-3773-

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