Universität zu Köln

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

Full text not available from this repository.

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
Creators:	Creators Email ORCID ORCID Put Code Wu, Liangliang UNSPECIFIED orcid.org/0000-0002-5434-0786 UNSPECIFIED Cao, Xiaoyan UNSPECIFIED orcid.org/0000-0002-3438-575X UNSPECIFIED Chen, Xuebo UNSPECIFIED UNSPECIFIED UNSPECIFIED Fang, Weihai UNSPECIFIED UNSPECIFIED UNSPECIFIED Dolg, Michael UNSPECIFIED orcid.org/0000-0002-0538-0837 UNSPECIFIED
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
Uncontrolled Keywords:	Keywords Language H BOND ACTIVATION; ELECTRONIC-STRUCTURE; URANIUM COMPLEXES; CHEMISTRY; OXO; HYDROXYLATION; REACTIVITY; MOLECULES; CATALYSIS; ANALOGS Multiple languages Chemistry, Multidisciplinary Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/17326