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Controlled Photocatalytic Hydrocarbon Oxidation by Uranyl Complexes
Univ Edinburgh, EaStCHEM Sch Chem, Joseph Black Bldg, Edinburgh EH9 3FJ, Midlothian, Scotland.
Univ Edinburgh, EaStCHEM Sch Chem, Joseph Black Bldg, Edinburgh EH9 3FJ, Midlothian, Scotland.
Univ Edinburgh, EaStCHEM Sch Chem, Joseph Black Bldg, Edinburgh EH9 3FJ, Midlothian, Scotland.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Molecular Biomimetics.ORCID iD: /0000-0002-5615-3204
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2019 (English)In: ChemCatChem, ISSN 1867-3880, E-ISSN 1867-3899, Vol. 11, no 16, p. 3786-3790Article in journal (Refereed) Published
Abstract [en]

Controlled, photocatalytic C-H bond activations are key reactions in the toolkits of the modern synthetic chemist. While it is known that the uranyl(VI) ion, [(UO2)-O-VI](2+), the environmentally dominant form of uranium, is photoactive, most literature examines its luminescent properties, neglecting its potential synthetic utility for photocatalytic C-H bond cleavage. Here, we synthesise and fully characterise an air-stable and hydrocarbon-soluble uranyl phenanthroline complex, [(UO2)-O-VI(NO3)(2)(Ph(2)phen)], U-Ph2phen, and demonstrate that it can catalytically abstract hydrogen atoms from a variety of organic substrates under visible light irradiation. We show that the commercially available parent complex, uranyl nitrate ([(UO2)-O-VI(NO3)(2)(OH2)(2)]center dot 4H(2)O; U-NO3), is also competent, but from electronic spectroscopy we attribute the higher rates and selectivity of U-Ph2phen to ligand-mediated electronic effects. Ketones are selectively formed over other oxygenated products (alcohols, etc.), and the catalytic oxidation of substrates containing a benzylic C-H position is particularly improved for U-Ph2phen. We also show uranyl-mediated photocatalytic C-C bond cleavage in a model lignin compound for the first time.

Place, publisher, year, edition, pages
Wiley-VCH Verlagsgesellschaft, 2019. Vol. 11, no 16, p. 3786-3790
Keywords [en]
Actinides, C-H bond activation, fluorescence spectroscopy, photocatalysis, uranium
National Category
Inorganic Chemistry Physical Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-400103DOI: 10.1002/cctc.201900037ISI: 000498036500021OAI: oai:DiVA.org:uu-400103DiVA, id: diva2:1380881
Funder
EU, European Research Council, 740311Available from: 2019-12-19 Created: 2019-12-19 Last updated: 2019-12-19Bibliographically approved

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