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Article Dans Une Revue JACS Au Année : 2022

Electron Shuttle in N-Heteroaromatic Ni Catalysts for Alkene Isomerization

Résumé

Simple N-heteroaromatic Ni(II) precatalysts, (L)NiMe2 (L = bipy, bipym), were used for alkene isomerization. With an original reduction method using a simple borane (HB(Cat)), a low-valent Ni center was formed readily and showed good conversion when a reducing divalent lanthanide fragment, Cp*2Yb, was coordinated to the (bipym)NiMe2 complex, a performance not achieved by the monometallic (bipy)NiMe2 analogue. Experimental mechanistic investigations and computational studies revealed that the redox non-innocence of the L ligand triggered an electron shuttle process, allowing the elusive formation of Ni(I) species that were central to the isomerization process. Additionally, the reaction occurred with a preference for mono-isomerization rather than chain-walking isomerization. The presence of the low-valent ytterbium fragment, which contributed to the formation of the electron shuttle, strongly stabilized the catalysts, allowing catalytic loading as low as 0.5%. A series of alkenes with various architectures have been tested. The possibility to easily tune the various components of the heterobimetallic catalyst reported here, the ligand L and the divalent lanthanide fragment, opens perspectives for further applications in catalysis induced by Ni(I) species.
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Dates et versions

hal-03768030 , version 1 (07-10-2022)

Identifiants

Citer

Maxime Tricoire, Ding Wang, Thayalan Rajeshkumar, Laurent Maron, Grégory Danoun, et al.. Electron Shuttle in N-Heteroaromatic Ni Catalysts for Alkene Isomerization. JACS Au, 2022, 2 (8), pp.1881-1888. ⟨10.1021/jacsau.2c00251⟩. ⟨hal-03768030⟩
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