Controlled Photocatalytic Hydrocarbon Oxidation by Uranyl Complexes

Polly L. Arnold, Jamie M. Purkis, Ryte Rutkauskaite, Daniel Kovacs, Jason B. Love, Jonathan Austin

Research output: Contribution to journalArticlepeer-review

Abstract

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 (UVIO22+), 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 organicsoluble uranyl phenanthroline complex, [UO2(NO3)2(Ph2phen)], UPh2phen, 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, UNO3 is also competent, but using electronic spectroscopy we attribute the higher rates and selectivity of UPh2phen 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 UPh2phen. We also show uranyl-mediated photocatalytic C-C bond cleavage in a model lignin compound for the first time.
Original languageEnglish
JournalChemCatChem
Early online date28 Feb 2019
DOIs
Publication statusE-pub ahead of print - 28 Feb 2019

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