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Controlled photocatalytic hydrocarbon oxidation by uranyl complexes

Controlled photocatalytic hydrocarbon oxidation by uranyl complexes
Controlled photocatalytic hydrocarbon oxidation by uranyl complexes
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, [UVIO2]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, [UVIO2(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 ([UVIO2(NO3)2(OH2)2]⋅4H2O; UNO3), is also competent, but from 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.
1867-3880
3786-3790
Arnold, Polly L.
431d494e-712d-4677-9ee2-0bcefe8a5ca0
Purkis, Jamie M.
17c76efb-2aa2-429e-92b3-5a21de7b02a5
Rutkauskaite, Ryte
dbcb6635-75f6-4683-a31d-d4e207a02a40
Kovacs, Daniel
f4823c4f-65da-47d3-8203-4b2649c6606a
Love, Jason B.
86349ecb-c5c7-4151-bd43-d79ddd214b27
Austin, Jonathan
9b92c945-1162-4785-ad11-c77f270cbf1d
Arnold, Polly L.
431d494e-712d-4677-9ee2-0bcefe8a5ca0
Purkis, Jamie M.
17c76efb-2aa2-429e-92b3-5a21de7b02a5
Rutkauskaite, Ryte
dbcb6635-75f6-4683-a31d-d4e207a02a40
Kovacs, Daniel
f4823c4f-65da-47d3-8203-4b2649c6606a
Love, Jason B.
86349ecb-c5c7-4151-bd43-d79ddd214b27
Austin, Jonathan
9b92c945-1162-4785-ad11-c77f270cbf1d

Arnold, Polly L., Purkis, Jamie M., Rutkauskaite, Ryte, Kovacs, Daniel, Love, Jason B. and Austin, Jonathan (2019) Controlled photocatalytic hydrocarbon oxidation by uranyl complexes. ChemCatChem, 11 (16), 3786-3790. (doi:10.1002/cctc.v11.16).

Record type: Article

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, [UVIO2]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, [UVIO2(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 ([UVIO2(NO3)2(OH2)2]⋅4H2O; UNO3), is also competent, but from 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.

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More information

Published date: 21 August 2019

Identifiers

Local EPrints ID: 435931
URI: http://eprints.soton.ac.uk/id/eprint/435931
ISSN: 1867-3880
PURE UUID: 01e12b23-9d37-4caf-8fce-55428c3d3d79
ORCID for Jamie M. Purkis: ORCID iD orcid.org/0000-0002-6387-1220

Catalogue record

Date deposited: 25 Nov 2019 17:30
Last modified: 26 Nov 2021 03:20

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Contributors

Author: Polly L. Arnold
Author: Jamie M. Purkis ORCID iD
Author: Ryte Rutkauskaite
Author: Daniel Kovacs
Author: Jason B. Love
Author: Jonathan Austin

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