Electron Shuttle in N-Heteroaromatic Ni Catalysts for Alkene Isomerization

Abstract

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.