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Phosphine Ligand Hemilability as a Route Towards Robust and Efficient Hydrogenation with Mn(I) Complexes

submitted on 21.04.2020, 15:40 and posted on 22.04.2020, 12:40 by Wenjun Yang, Ivan Yu. Chernyshov, Robin K. A. van Schendel, Manuela Weber, Christian Müller, Georgy Filonenko, Evgeny Pidko
The foremost requirement for any catalyst to be
implemented in practice is its efficiency and stability. This
requirement is particularly valid for manganese hydrogenation catalysts representing more sustainable alternatives to conventional noble metal-based systems. Herein, we report a highly efficient Mn(I)-CNP pre-catalyst featuring phosphine arm hemilability, which gives rise to the excellent productivity (TOF° up to 41 000 h-1) and outstanding stability (TON up to 200 000) in hydrogenation catalysis. This system enables near-quantitative hydrogenation of ketones, imines, aldehydes, and esters at the catalyst loadings as low as 5-200 ppm. Our analysis points to the crucial role of the phosphine hemilability for the catalyst activation step and the stability of the reactive species under the catalytic conditions. Unprecedented in
manganese hydrogenation catalysis, this unusual coordination behavior might have general utility for improving catalysis by Mn complexes and bringing them yet another competitive advantage.


ERC Horizon 2020 research and innovation program Grant no. 725686


Email Address of Submitting Author


Delft University of Technology


The Netherlands

ORCID For Submitting Author


Declaration of Conflict of Interest

No conflict of interests declared

Version Notes

This is the original preprint posted after submission to the journal