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Mapping the mechanisms of oxidative addition in cross-coupling reactions catalysed by phosphine-ligated Ni(0)

Nature Chemistry (2024)Cite this article

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Abstract

The complexes of first-row transition metals can undergo elementary reactions by multiple pathways due to their propensity to undergo both one- and two-electron redox steps. Classic and recent studies of the oxidative addition of aryl halides to Ni(0)—a common step in widely practised cross-coupling processes—have yielded contradictory conclusions about stepwise, radical versus concerted mechanisms, but such information is crucial to the design of catalysts based on earth-abundant metals. Here we show that the oxidative addition of aryl halides to Ni(0) ligated by monophosphines occurs by both mechanisms and delineate how the branching of radical and non-radical pathways depends on the electronic properties of both the ligand and reactant arene as well as the identity of the halide. The one-electron pathway occurs by outer-sphere electron transfer to form an aryl radical rather than the often-proposed halogen atom transfer.

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Fig. 1: Studies of the oxidative addition of aryl halides to monodentate phosphine-ligated Ni(0) and their conclusions.
Fig. 2: Competition experiments to distinguish between oxidative addition by electron transfer or concerted pathways.
Fig. 3: Experimental design and results of the oxidative addition of aryl halide 5 containing a trap for aryl radicals.
Fig. 4: Oxidative addition of aryl iodides by electron transfer or halogen abstraction.
Fig. 5: Hammett analysis of the oxidative addition of 2-iodo-1,3-diisopropylbenzenes to Ni(PEt3)4.
Fig. 6: Variation in the fraction of product from oxidative addition with reaction potential.

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Data availability

The data supporting the findings of this study are available in the Supplementary Information. The crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre under deposition numbers CCDC 2255308 (NiI(PEt3)3), 2255309 (NiCl(PPh3)3) and 2255310 (6a-I).

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Acknowledgements

We thank I. Yu for assistance in collecting data and for solving the crystal structures, J. Brunn for help with obtaining HRMS data, Z. Zhou at the UC Berkeley QB3 Chemistry Mass Spectrometry Facility for help in obtaining HRMS data, J. Nicolai for assistance with the graphics, and both J. Brunn and C. Delaney for discussions during the preparation of the paper. This work was supported by the NIGMS of the NIH under R35GM130387. We thank the National Science Foundation for a Graduate Research Fellowship to C.N.P. We acknowledge the UC Berkeley NMR Facility and the National Institutes of Health for providing funding for the cryoprobe for the AV-600 spectrometer under grant number S10OD024998.

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Authors and Affiliations

  1. University of California, Berkeley, CA, USA

    Christina N. Pierson & John F. Hartwig

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  1. Christina N. Pierson
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  2. John F. Hartwig
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Contributions

J.F.H. and C.N.P. conceived and designed the initial research. C.N.P. performed the synthetic and competition experiments and conducted the kinetic studies. C.N.P. and J.F.H. designed and analysed the experiments and prepared the first draft of the paper. Both authors contributed to or approved the final version of the paper.

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Correspondence to John F. Hartwig.

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The authors declare no competing interests.

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Nature Chemistry thanks Marc-Etienne Moret and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Protocols, Figs. 1–135 and Table 1.

Supplementary Data 1

Crystallographic data file for 6a-I (CCDC number 2255310).

Supplementary Data 2

Crystallographic data file for NiCl(PPh3)3 (CCDC number 2255309).

Supplementary Data 3

Crystallographic data file for NiI(PEt3)3 (CCDC number 2255308).

Supplementary Data 4

Structure factor file for 6a-I (CCDC number 2255310).

Supplementary Data 5

Structure factor file for NiCl(PPh3)3 (CCDC number 2255309).

Supplementary Data 6

Structure factor file for NiI(PEt3)3 (CCDC number 2255308).

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Pierson, C.N., Hartwig, J.F. Mapping the mechanisms of oxidative addition in cross-coupling reactions catalysed by phosphine-ligated Ni(0). Nat. Chem. (2024). https://doi.org/10.1038/s41557-024-01451-x

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