Mechanistic implications for the Ni(I)-catalyzed Kumada cross-coupling reaction
- Herein we report on the cross-coupling reaction of phenylmagnesium bromide with aryl halides using the well-defined tetrahedral Ni(I) complex, [(Triphos)\(Ni^{I}Cl\)] (Triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane). In the presence of 0.5 mol % [(Triphos)\(Ni^{I}\)Cl], 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 [(\(\kappa^{2}-Triphos)Ni^{II}Cl_{2}\)] and [(\(\kappa^{3}-Triphos)Ni^{II}Cl\)](X) (X = ClO\(_4\), BF\(_4\)) 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.
Author: | Linda IfflandGND, Anette PetukerGND, Maurice van GastelGND, Ulf-Peter ApfelORCiDGND |
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URN: | urn:nbn:de:hbz:294-67270 |
DOI: | https://doi.org/10.3390/inorganics5040078 |
Parent Title (English): | Inorganics |
Publisher: | MDPI |
Place of publication: | Basel |
Document Type: | Article |
Language: | English |
Date of Publication (online): | 2019/11/14 |
Date of first Publication: | 2017/11/14 |
Publishing Institution: | Ruhr-Universität Bochum, Universitätsbibliothek |
Tag: | DFT; EPR; Grignard; cross-coupling; nickel; tripodal ligands |
Volume: | 5 |
Issue: | 4, Article 78 |
First Page: | 78-1 |
Last Page: | 78-13 |
Institutes/Facilities: | Lehrstuhl für Anorganische Chemie I, Bioanorganische Chemie |
Materials Research Department | |
Research Department Closed Carbon Cycle Economy | |
Research Department Interfacial Systems Chemistry | |
Lehrstuhl für Anorganische Chemie I, Aktivierung kleiner Moleküle | |
open_access (DINI-Set): | open_access |
faculties: | Fakultät für Chemie und Biochemie |
Licence (English): | Creative Commons - CC BY 4.0 - Attribution 4.0 International |