Hammarback, Lars Anders, Clark, Ian P., Sazanovich, Igor et al. (6 more authors) (2018) Mapping out the key carbon–carbon bond-forming steps in Mn-catalysed C–H functionalization. Nature Catalysis. pp. 830-840. ISSN 2520-1158
Abstract
Detailed understanding of the mechanistic processes that underpin transition metal-catalysed reactions allows for the rational and de novo development of complexes with enhanced activity, efficacy and wider substrate scope. Directly observing bond cleaving and forming events underpinning a catalytic reaction is non-trivial as the species that facilitate these steps are frequently short-lived and present at low concentrations. Here we describe how the photochemical activation of a manganese precatalyst, [Mn(ppy)(CO)4], results in selective loss of a carbonyl ligand simulating entry into the catalytic cycle for Mn-promoted C–H bond functionalisation. Time-resolved infra-red spectroscopy (ps-ms timescale) allows direct observation of the species responsible for the essential carbon-carbon bond formation step and an evaluation of the factors affecting its rate. The mechanistic information prompted discovery of a new photochemically initiated manganese-promoted coupling of phenylacetylene with 2-phenylpyrindine. This study provides unique insight into the mechanistic pathways which underpin catalysis by an Earth-abundant metal, manganese.
Metadata
Item Type: | Article |
---|---|
Authors/Creators: |
|
Copyright, Publisher and Additional Information: | © 2018 Springer Nature Limited. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details. |
Dates: |
|
Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Depositing User: | Pure (York) |
Date Deposited: | 08 Nov 2018 09:40 |
Last Modified: | 01 Jan 2025 00:09 |
Published Version: | https://doi.org/10.1038/s41929-018-0145-y |
Status: | Published |
Refereed: | Yes |
Identification Number: | 10.1038/s41929-018-0145-y |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:138380 |