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16-Electron Nickel(0)-Olefin Complexes in Low-Temperature C(sp2)–C(sp3) Kumada Cross-Couplings

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Lutz,  Sigrid
Research Group Cornellà, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Nattmann,  Lukas
Research Group Cornellà, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Nöthling,  Nils
Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Cornella,  Josep
Research Group Cornellà, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Lutz, S., Nattmann, L., Nöthling, N., & Cornella, J. (2021). 16-Electron Nickel(0)-Olefin Complexes in Low-Temperature C(sp2)–C(sp3) Kumada Cross-Couplings. Organometallics, 40(14), 2220-2230. doi:10.1021/acs.organomet.0c00775.


Cite as: http://hdl.handle.net/21.11116/0000-0009-169F-C
Abstract
Investigations into the mechanism of the low-temperature C(sp2)–C(sp3) Kumada cross-coupling catalyzed by highly reduced nickel-olefin-lithium complexes revealed that 16-electron tris(olefin)nickel(0) complexes are competent catalysts for this transformation. A survey of various nickel(0)-olefin complexes identified Ni(nor)3 as an active catalyst, with performance comparable to that of the previously described Ni-olefin-lithium precatalyst. We demonstrate that Ni(nor)3, however, is unable to undergo oxidative addition to the corresponding C(sp2)–Br bond at low temperatures (<−40 °C), thus indicating that the canonical cross-coupling cycle is not operative under this condition. Instead, such binary nickel(0)-olefin complexes capitalize on the long-known Lewis acidity of the Ni(0) center when it is coordinated to olefins to accommodate the incoming charge from the Grignard reagent, forming a nickel(0)-alkylmagnesium complex. We demonstrate that this unique heterobimetallic complex is now primed for reactivity, thus cleaving the C(sp2)–Br bond and ultimately delivering the C(sp2)–C(sp3) bond in high yields.