Wu, Liangliang ORCID: 0000-0002-5434-0786, Cao, Xiaoyan
ORCID: 0000-0002-3438-575X, Chen, Xuebo, Fang, Weihai and Dolg, Michael
ORCID: 0000-0002-0538-0837
(2018).
Visible-Light Photocatalysis of C(sp(3))-H Fluorination by the Uranyl Ion: Mechanistic Insights.
Angew. Chem.-Int. Edit., 57 (36).
S. 11812 - 11817.
WEINHEIM:
WILEY-V C H VERLAG GMBH.
ISSN 1521-3773
Abstract
The uranyl dication shows photocatalytic activity towards C(sp(3))-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.
Item Type: | Journal Article | ||||||||||||||||||||||||
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URN: | urn:nbn:de:hbz:38-173261 | ||||||||||||||||||||||||
DOI: | 10.1002/anie.201806554 | ||||||||||||||||||||||||
Journal or Publication Title: | Angew. Chem.-Int. Edit. | ||||||||||||||||||||||||
Volume: | 57 | ||||||||||||||||||||||||
Number: | 36 | ||||||||||||||||||||||||
Page Range: | S. 11812 - 11817 | ||||||||||||||||||||||||
Date: | 2018 | ||||||||||||||||||||||||
Publisher: | WILEY-V C H VERLAG GMBH | ||||||||||||||||||||||||
Place of Publication: | WEINHEIM | ||||||||||||||||||||||||
ISSN: | 1521-3773 | ||||||||||||||||||||||||
Language: | English | ||||||||||||||||||||||||
Faculty: | Faculty of Mathematics and Natural Sciences | ||||||||||||||||||||||||
Divisions: | Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Theoretical Chemistry | ||||||||||||||||||||||||
Subjects: | no entry | ||||||||||||||||||||||||
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Refereed: | Yes | ||||||||||||||||||||||||
URI: | http://kups.ub.uni-koeln.de/id/eprint/17326 |
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