Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 57, Issue 36, Pages 11812-11816Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201806554
Keywords
abinitio calculations; C-H activation; photocatalysis; single-electron transfer; uranium
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Funding
- China Scholarship Council (CSC)
- DFG [CA1390/1-1, DO440/10-1]
- [NSFC21725303]
- [NSFC21421003]
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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.
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