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

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.

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 Creators:
Lutz, Sigrid1, Author           
Nattmann, Lukas1, Author           
Nöthling, Nils2, Author           
Cornella, Josep1, Author           
Affiliations:
1Research Group Cornellà, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2466693              
2Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445625              

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 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.

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Language(s): eng - English
 Dates: 2020-12-082021-03-262021-07-26
 Publication Status: Published in print
 Pages: 11
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/acs.organomet.0c00775
 Degree: -

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Title: Organometallics
  Abbreviation : Organometallics
Source Genre: Journal
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Publ. Info: Washington, D.C. : American Chemical Society
Pages: - Volume / Issue: 40 (14) Sequence Number: - Start / End Page: 2220 - 2230 Identifier: ISSN: 0276-7333
CoNE: https://pure.mpg.de/cone/journals/resource/954925505259