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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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).
References
Labinger, J. A. Tutorial on oxidative addition. Organometallics 34, 4784–4795 (2015).
Campeau, L.-C. & Hazari, N. Cross-coupling and related reactions: connecting past success to the development of new reactions for the future. Organometallics 38, 3–35 (2019).
Hartwig, J. F. Organotransition Metal Chemistry: From Bonding to Catalysis (Univ. Science Books, 2010).
Lundgren, R. J. & Stradiotto, M. Addressing challenges in palladium-catalyzed cross-coupling reactions through ligand design. Chem. Eur. J. 18, 9758–9769 (2012).
Ananikov, V. P. Nickel: the “spirited horse” of transition metal catalysis. ACS Catal. 5, 1964–1971 (2015).
Tasker, S. Z., Standley, E. A. & Jamison, T. F. Recent advances in homogeneous nickel catalysis. Nature 509, 299–309 (2014).
Diccianni, J. B. & Diao, T. Mechanisms of nickel-catalyzed cross-coupling reactions. Trends Chem. 1, 830–844 (2019).
Ting, S. I., Williams, W. L. & Doyle, A. G. Oxidative addition of aryl halides to a Ni(I)–bipyridine complex. J. Am. Chem. Soc. 144, 5575–5582 (2022).
Lin, Q. & Diao, T. Mechanism of Ni-catalyzed reductive 1,2-dicarbofunctionalization of alkenes. J. Am. Chem. Soc. 141, 17937–17948 (2019).
Till, N. A., Oh, S., MacMillan, D. W. C. & Bird, M. J. The application of pulse radiolysis to the study of Ni(I) intermediates in Ni-catalyzed cross-coupling reactions. J. Am. Chem. Soc. 143, 9332–9337 (2021).
Yakhvarov, D. G., Budnikova, Y. H. & Sinyashin, O. G. Kinetic features of oxidative addition of organic halides to the organonickel σ-complex. Russ. Chem. Bull. 52, 567–569 (2003).
Kawamata, Y. et al. Electrochemically driven, Ni-catalyzed aryl amination: scope, mechanism, and applications. J. Am. Chem. Soc. 141, 6392–6402 (2019).
Sun, R. et al. Elucidation of a redox-mediated reaction cycle for nickel-catalyzed cross coupling. J. Am. Chem. Soc. 141, 89–93 (2019).
Durandetti, M., Devaud, M. & Perichon, J. Investigation of the reductive coupling of aryl halides and/or ethylchloroacetate electrocatalyzed by the precursor NiX 2 (bpy) with X- = Cl-, Br- or MeSO3- and bpy = 2,2′-dipyridyl. New J. Chem. 20, 659–667 (1996).
Tsou, T. T. & Kochi, J. K. Mechanism of oxidative addition. Reaction of nickel(0) complexes with aromatic halides. J. Am. Chem. Soc. 101, 6319–6332 (1979).
Bajo, S., Laidlaw, G., Kennedy, A. R., Sproules, S. & Nelson, D. J. Oxidative addition of aryl electrophiles to a prototypical nickel(0) complex: mechanism and structure/reactivity relationships. Organometallics 36, 1662–1672 (2017).
Beromi, M. M. et al. Mechanistic study of an improved Ni precatalyst for Suzuki–Miyaura reactions of aryl sulfamates: understanding the role of Ni(I) species. J. Am. Chem. Soc. 139, 922–936 (2017).
Pérez-García, P. M. et al. Oxidative addition of aryl halides to a triphosphine Ni(0) center to form pentacoordinate Ni(II) aryl species. Organometallics 39, 1139–1144 (2020).
Funes‐Ardoiz, I., Nelson, D. J. & Maseras, F. Halide abstraction competes with oxidative addition in the reactions of aryl halides with [Ni(PMenPh(3−n))4]. Chem. Eur. J. 23, 16728–16733 (2017).
Tye, J. W., Weng, Z., Johns, A. M., Incarvito, C. D. & Hartwig, J. F. Copper complexes of anionic nitrogen ligands in the amidation and imidation of aryl halides. J. Am. Chem. Soc. 130, 9971–9983 (2008).
Zenkina, O. V., Gidron, O., Shimon, L. J. W., Iron, M. A. & van der Boom, M. E. Mechanistic aspects of aryl–halide oxidative addition, coordination chemistry, and ring-walking by palladium. Chem. Eur. J. 21, 16113–16125 (2015).
Enemærke, R. J., Christensen, T. B., Jensen, H. & Daasbjerg, K. Application of a new kinetic method in the investigation of cleavage reactions of haloaromatic radical anions. J. Chem. Soc. Perkin Trans. 2 2001, 1620–1630 (2001).
Newcomb, M. in Encyclopedia of Radicals in Chemistry, Biology and Materials (eds Chatgilialoglu, C. & Studer, A.) 107–124 (John Wiley & Sons, 2012).
Manzoor, A., Wienefeld, P., Baird, M. C. & Budzelaar, P. H. M. Catalysis of cross-coupling and homocoupling reactions of aryl halides utilizing Ni(0), Ni(I), and Ni(II) precursors; Ni(0) compounds as the probable catalytic species but Ni(I) compounds as intermediates and products. Organometallics 36, 3508–3519 (2017).
Branchi, B., Galli, C., Gentili, P., Marinelli, M. & Mencarelli, P. A radical and an electron transfer process are compared in their regioselectivities towards a molecule with two different C−I bonds: effect of steric congestion. Eur. J. Org. Chem. 2000, 2663–2668 (2000).
Takeda, N., Poliakov, P. V., Cook, A. R. & Miller, J. R. Faster dissociation: measured rates and computed effects on barriers in aryl halide radical anions. J. Am. Chem. Soc. 126, 4301–4309 (2004).
Rohrbach, S. et al. Concerted nucleophilic aromatic substitution reactions. Angew. Chem. Int. Ed. 58, 16368–16388 (2019).
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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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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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. Map** the mechanisms of oxidative addition in cross-coupling reactions catalysed by phosphine-ligated Ni(0). Nat. Chem. 16, 930–937 (2024). https://doi.org/10.1038/s41557-024-01451-x
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DOI: https://doi.org/10.1038/s41557-024-01451-x
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