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Inorganics 2017, 5(4), 78; doi:10.3390/inorganics5040078

Mechanistic Implications for the Ni(I)-Catalyzed Kumada Cross-Coupling Reaction

Anorganische Chemie I, Ruhr-Universität Bochum, Universitätsstraße 150, 44801 Bochum, Germany
Max-Planck-Institut für Chemische Energiekonversion, Stiftstraße 34-36, 45470 Mülheim, Germany
Author to whom correspondence should be addressed.
Received: 9 October 2017 / Revised: 7 November 2017 / Accepted: 10 November 2017 / Published: 14 November 2017
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Herein we report on the cross-coupling reaction of phenylmagnesium bromide with aryl halides using the well-defined tetrahedral Ni(I) complex, [(Triphos)NiICl] (Triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane). In the presence of 0.5 mol % [(Triphos)NiICl], good to excellent yields (75–97%) of the respective coupling products within a reaction time of only 2.5 h at room temperature were achieved. Likewise, the tripodal Ni(II)complexes [(κ2-Triphos)NiIICl2] and [(κ3-Triphos)NiIICl](X) (X = ClO4, BF4) were tested as potential pre-catalysts for the Kumada cross-coupling reaction. While the Ni(II) complexes also afford the coupling products in comparable yields, mechanistic investigations by UV/Vis and electron paramagnetic resonance (EPR) spectroscopy indicate a Ni(I) intermediate as the catalytically active species in the Kumada cross-coupling reaction. Based on experimental findings and density functional theory (DFT) calculations, a plausible Ni(I)-catalyzed reaction mechanism for the Kumada cross-coupling reaction is presented. View Full-Text
Keywords: nickel; tripodal ligands; cross-coupling; EPR; Grignard; DFT nickel; tripodal ligands; cross-coupling; EPR; Grignard; DFT

This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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MDPI and ACS Style

Iffland, L.; Petuker, A.; van Gastel, M.; Apfel, U.-P. Mechanistic Implications for the Ni(I)-Catalyzed Kumada Cross-Coupling Reaction. Inorganics 2017, 5, 78.

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