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Issue 8, 2021
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Boosting homogeneous chemoselective hydrogenation of olefins mediated by a bis(silylenyl)terphenyl-nickel(0) pre-catalyst

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Abstract

The isolable chelating bis(N-heterocyclic silylenyl)-substituted terphenyl ligand [SiII(Terp)SiII] as well as its bis(phosphine) analogue [PIII(Terp)PIII] have been synthesised and fully characterised. Their reaction with Ni(cod)2 (cod = cycloocta-1,5-diene) affords the corresponding 16 VE nickel(0) complexes with an intramolecular η2-arene coordination of Ni, [E(Terp)E]Ni(η2-arene) (E = PIII, SiII; arene = phenylene spacer). Due to a strong cooperativity of the Si and Ni sites in H2 activation and H atom transfer, [SiII(Terp)SiII]Ni(η2-arene) mediates very effectively and chemoselectively the homogeneously catalysed hydrogenation of olefins bearing functional groups at 1 bar H2 pressure and room temperature; in contrast, the bis(phosphine) analogous complex shows only poor activity. Catalytic and stoichiometric experiments revealed the important role of the η2-coordination of the Ni(0) site by the intramolecular phenylene with respect to the hydrogenation activity of [SiII(Terp)SiII]Ni(η2-arene). The mechanism has been established by kinetic measurements, including kinetic isotope effect (KIE) and Hammet-plot correlation. With this system, the currently highest performance of a homogeneous nickel-based hydrogenation catalyst of olefins (TON = 9800, TOF = 6800 h−1) could be realised.

Graphical abstract: Boosting homogeneous chemoselective hydrogenation of olefins mediated by a bis(silylenyl)terphenyl-nickel(0) pre-catalyst

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Article information


Submitted
25 Nov 2020
Accepted
04 Jan 2021
First published
08 Jan 2021

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2021,12, 2909-2915
Article type
Edge Article

Boosting homogeneous chemoselective hydrogenation of olefins mediated by a bis(silylenyl)terphenyl-nickel(0) pre-catalyst

M. Lücke, S. Yao and M. Driess, Chem. Sci., 2021, 12, 2909
DOI: 10.1039/D0SC06471H

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