The highly surprising behaviour of diphosphine ligands in iron-catalysed Negishi cross-coupling

Messinis, A. M. et al. (2019) The highly surprising behaviour of diphosphine ligands in iron-catalysed Negishi cross-coupling. Nature Catalysis, 2, pp. 123-133. (doi: 10.1038/s41929-018-0197-z)

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Iron-catalysed cross-coupling is undergoing explosive development, but mechanistic understanding lags far behind synthetic methodology. Here, we find that the activity of iron–diphosphine pre-catalysts in the Negishi coupling of benzyl halides is strongly dependent on the diphosphine, but the ligand does not appear to be coordinated to the iron during turnover. This was determined using time-resolved in operando X-ray absorption fine structure spectroscopy employing a custom-made flow cell and confirmed by 31P NMR spectroscopy. While the diphosphine ligands tested are all able to coordinate to iron(II), in the presence of excess zinc(II)—as in the catalytic reaction—they coordinate predominantly to the zinc. Furthermore, combined synthetic and kinetic investigations implicate the formation of a putative mixed Fe–Zn(dpbz) species before the rate-limiting step of catalysis. These unexpected findings may not only impact the field of iron-catalysed Negishi cross-coupling, but potentially beyond to reactions catalysed by other transition metal/diphosphine complexes.

Item Type:Articles
Glasgow Author(s) Enlighten ID:Gibson, Dr Emma
Authors: Messinis, A. M., Luckham, S. L.J., Wells, P. P., Gianolio, D., Gibson, E. K., O’Brien, H. M., Sparkes, H. A., Davis, S. A., Callison, J., Elorriaga, D., Hernandez-Fajardo, O., and Bedford, R. B.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Nature Catalysis
Publisher:Nature Research
ISSN (Online):2520-1158
Published Online:31 December 2018
Copyright Holders:Copyright © 2018 Springer Nature Publishing AG
First Published:First published in Nature Catalysis 2018
Publisher Policy:Reproduced in accordance with the copyright policy of the publisher

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
652891Towards closing the chlorine cycle in large-scale chemical manufacturing processes (UK Catalysis hub)David LennonEngineering and Physical Sciences Research Council (EPSRC)EP/K014854/1CHEM - CHEMISTRY