Mapping out the key carbon–carbon bond-forming steps in Mn-catalysed C–H functionalization

Lars Anders Hammarback, Ian P. Clark, Igor Sazanovich, Michael Towrie, Alan Robinson, Francis Clarke, Stephanie Meyer, Ian James Stewart Fairlamb, Jason Martin Lynam

Research output: Contribution to journalArticlepeer-review


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.
Original languageEnglish
Pages (from-to)830-840
Number of pages11
JournalNature Catalysis
Issue number11
Early online date8 Oct 2018
Publication statusPublished - 1 Nov 2018

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