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] (ppy = 2-phenylpyridine), results in selective loss of a carbonyl ligand simulating entry into the catalytic cycle for manganese-promoted C–H bond functionalization. Time-resolved infrared spectroscopy (on the ps–ms timescale) allows direct observation of the species responsible for the essential C–C bond formation step and an evaluation of the factors affecting its rate. This mechanistic information prompted the discovery of a new photochemically initiated manganese-promoted coupling of phenylacetylene with 2-phenylpyridine. This study provides unique insight into the mechanistic pathways underpinning catalysis by an Earth-abundant metal, manganese.
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All data supporting this study are available on request from the University of York’s York Research Database: https://doi.org/10.15124/46f25600-736a-408a-b498-8b7f6a5f3f2e. X-ray crystallography data for structures 3 and 4 are available free of charge from the Cambridge Crystallographic Data Centre (https://www.ccdc.cam.ac.uk/) under reference numbers 1815767 and 1844072, respectively.
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We are grateful to Syngenta and the Engineering and Physical Sciences Research Council (CASE studentship to L.A.H. (EP/N509413/) and, for the computational equipment used in this study, EP/H011455/, and Engineering and Physical Sciences Research Council ‘ENERGY’ grant EP/K031589/1) for funding, as well as the Science and Technology Facilities Council for access to the ULTRA facilities at the Rutherford Appleton Laboratory. We thank A. Whitwood and R. Bean for the X-ray structure of compounds 3 and 4, D. Turnbull for a crystalline sample of 4, and R. Perutz for insightful comments on this work.
The authors declare no competing interests
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Hammarback, L.A., Clark, I.P., Sazanovich, I.V. et al. Mapping out the key carbon–carbon bond-forming steps in Mn-catalysed C–H functionalization. Nat Catal 1, 830–840 (2018). https://doi.org/10.1038/s41929-018-0145-y
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