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

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Original languageEnglish
Pages (from-to)123-133
Number of pages11
JournalNature Catalysis
Volume2
Issue number2
Early online date31 Dec 2018
DOIs
DateAccepted/In press - 9 Nov 2018
DateE-pub ahead of print - 31 Dec 2018
DatePublished (current) - 1 Feb 2019

Abstract

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 31 P 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.

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  • Full-text PDF (accepted author manuscript)

    Rights statement: This is the author accepted manuscript (AAM). The final published version (version of record) is available online via Nature at https://doi.org/10.1038/s41929-018-0197-z . Please refer to any applicable terms of use of the publisher.

    Accepted author manuscript, 2 MB, PDF document

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