article published yes Lucia Anghileri author 7b65e46e-1f51-11f0-8ea0-faa153157f5e Haralds Baunis author 2eea55ec-e8ec-11ed-86cb-d9c76787acfe Aleksander Bena author 4197c39e-e8ec-11ed-86cb-afed934cd664 Christos Giannoudis author 1bd506c6-e8ec-11ed-86cb-d495f63f2dcd John H. Burke author Susanne Reischauer author Christoph Merschjann author Rachel F. Wallick author Tarek Al Said author Callum E Adams author 126d6d0f-fdc1-11ee-bb4a-9f462709fa9d Gianluca Simionato author Sergey Kovalenko author Luca Dell’Amico author Renske M. Van Der Veen author Bartholomäus Pieber author 93e5e5b2-0da6-11ed-8a41-af589a0247260000-0001-8689-388X BaPi department Photoactive ligands for transformative nickel catalysis project Advances in nickel catalysis have significantly broadened the synthetic chemists’ toolbox, particularly through methodologies leveraging paramagnetic nickel species via photoredox catalysis or electrochemistry. Key to these reactions is the oxidation state modulation of nickel via single-electron transfer events. Recent mechanistic studies indicate that C(sp2)–heteroatom bond formations proceed through NiI/NiIII cycles. Related C(sp2)–C(sp3) cross-couplings operate via the photocatalytic generation of C-centered radicals and a catalytic cycle that involves Ni0, NiI, and NiIII species. Here, we show that light-mediated nickel-catalyzed C(sp2)–C(sp3) bond formations can be carried out without using exogenous photoredox catalysts but with a photoactive ligand. In a pursuit of expanding the scope of C(sp2)–heteroatom couplings using donor–acceptor ligands, we identified a photoactive nickel complex capable of catalyzing cross-couplings between aryl halides and benzyltrifluoroborate salts. Mechanistic investigations provide evidence that transmetalation between a photochemically generated NiI species and the organoboron compound is the key catalytic step in a NiI/NiIII catalytic cycle under these conditions. https://research-explorer.ista.ac.at/download/19599/20137/2025_JACS_Anghileri.pdf application/pdfno American Chemical Society2025 eng 0002-7863 1520-5126 40211781 00146585800000110.1021/jacs.4c16050 1471613169–13179 Anghileri, Lucia, Haralds Baunis, Aleksander Bena, Christos Giannoudis, John H. Burke, Susanne Reischauer, Christoph Merschjann, et al. “Evidence for a Unifying NiI/NiIII Mechanism in Light-Mediated Cross-Coupling Catalysis.” <i>Journal of the American Chemical Society</i>. American Chemical Society, 2025. <a href="https://doi.org/10.1021/jacs.4c16050">https://doi.org/10.1021/jacs.4c16050</a>. Anghileri L, Baunis H, Bena A, et al. Evidence for a unifying NiI/NiIII mechanism in light-mediated cross-coupling catalysis. <i>Journal of the American Chemical Society</i>. 2025;147(16):13169–13179. doi:<a href="https://doi.org/10.1021/jacs.4c16050">10.1021/jacs.4c16050</a> L. Anghileri, H. Baunis, A. Bena, C. Giannoudis, J.H. Burke, S. Reischauer, C. Merschjann, R.F. Wallick, T. Al Said, C.E. Adams, G. Simionato, S. Kovalenko, L. Dell’Amico, R.M. Van Der Veen, B. Pieber, Journal of the American Chemical Society 147 (2025) 13169–13179. Anghileri, L., Baunis, H., Bena, A., Giannoudis, C., Burke, J. H., Reischauer, S., … Pieber, B. (2025). Evidence for a unifying NiI/NiIII mechanism in light-mediated cross-coupling catalysis. <i>Journal of the American Chemical Society</i>. American Chemical Society. <a href="https://doi.org/10.1021/jacs.4c16050">https://doi.org/10.1021/jacs.4c16050</a> Anghileri L, Baunis H, Bena A, Giannoudis C, Burke JH, Reischauer S, Merschjann C, Wallick RF, Al Said T, Adams CE, Simionato G, Kovalenko S, Dell’Amico L, Van Der Veen RM, Pieber B. 2025. Evidence for a unifying NiI/NiIII mechanism in light-mediated cross-coupling catalysis. Journal of the American Chemical Society. 147(16), 13169–13179. Anghileri, Lucia, et al. “Evidence for a Unifying NiI/NiIII Mechanism in Light-Mediated Cross-Coupling Catalysis.” <i>Journal of the American Chemical Society</i>, vol. 147, no. 16, American Chemical Society, 2025, pp. 13169–13179, doi:<a href="https://doi.org/10.1021/jacs.4c16050">10.1021/jacs.4c16050</a>. L. Anghileri <i>et al.</i>, “Evidence for a unifying NiI/NiIII mechanism in light-mediated cross-coupling catalysis,” <i>Journal of the American Chemical Society</i>, vol. 147, no. 16. American Chemical Society, pp. 13169–13179, 2025. 195992025-04-20T22:01:28Z2025-10-02T08:22:12Z