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Open AccessArticle

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

1
Anorganische Chemie I, Ruhr-Universität Bochum, Universitätsstraße 150, 44801 Bochum, Germany
2
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
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
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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. https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics5040078

AMA 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(4):78. https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics5040078

Chicago/Turabian Style

Iffland, Linda; Petuker, Anette; Van Gastel, Maurice; Apfel, Ulf-Peter. 2017. "Mechanistic Implications for the Ni(I)-Catalyzed Kumada Cross-Coupling Reaction" Inorganics 5, no. 4: 78. https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics5040078

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