Unveiling the mechanism of triphos-Ru catalysed C–O bond disconnections in polymers

Alexander Ahrens; Gabriel Martins Ferreira Batista; Hans Christian D. Hammershøj; Emil Vincent Schwibinger; Ainara Nova; Troels Skrydstrup

doi:10.1038/s41467-024-50083-9

Unveiling the mechanism of triphos-Ru catalysed C–O bond disconnections in polymers

Alexander Ahrens^*, Gabriel Martins Ferreira Batista, Hans Christian D. Hammershøj, Emil Vincent Schwibinger, Ainara Nova^*, Troels Skrydstrup^*

^*Corresponding author for this work

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

Abstract

Ruthenium complexes with facially coordinating tripodal phosphine ligands are privileged catalysts for a broad range of (de-)hydrogenation-based transformations. Among these, C–O bond hydrogenolysis holds potential for the depolymerisation of both the biopolymer lignin and epoxy resins applied in wind turbine blades, aircrafts and more. However, this methodology is poorly understood in mechanistic terms. Here, we present a detailed investigation on the triphos-Ru catalysed C–O bond scission on a molecular level. A combination of experimental, spectroscopical and theoretical studies elucidates the reactivity of the ruthenium trimethylenemethane precatalyst, revealing the key roles of ruthenium phenolates in both catalyst activation as well as the catalytic cycle itself. Furthermore, a Ru(0)/Ru(II) oxidative addition into the C–O bond is disclosed, with a triphos-Ru(0) dihydrogen complex as entry point. With the molecular nature of the operating triphos-Ru species and the thermodynamics and kinetics of the catalysis unravelled, improvements of established methods as well as design of related transformations may become possible.

Original language	English
Article number	5656
Journal	Nature Communications
Volume	15
ISSN	2041-1723
DOIs	https://doi.org/10.1038/s41467-024-50083-9
Publication status	Published - Jul 2024

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title = "Unveiling the mechanism of triphos-Ru catalysed C–O bond disconnections in polymers",

abstract = "Ruthenium complexes with facially coordinating tripodal phosphine ligands are privileged catalysts for a broad range of (de-)hydrogenation-based transformations. Among these, C–O bond hydrogenolysis holds potential for the depolymerisation of both the biopolymer lignin and epoxy resins applied in wind turbine blades, aircrafts and more. However, this methodology is poorly understood in mechanistic terms. Here, we present a detailed investigation on the triphos-Ru catalysed C–O bond scission on a molecular level. A combination of experimental, spectroscopical and theoretical studies elucidates the reactivity of the ruthenium trimethylenemethane precatalyst, revealing the key roles of ruthenium phenolates in both catalyst activation as well as the catalytic cycle itself. Furthermore, a Ru(0)/Ru(II) oxidative addition into the C–O bond is disclosed, with a triphos-Ru(0) dihydrogen complex as entry point. With the molecular nature of the operating triphos-Ru species and the thermodynamics and kinetics of the catalysis unravelled, improvements of established methods as well as design of related transformations may become possible.",

author = "Alexander Ahrens and Batista, {Gabriel Martins Ferreira} and Hammersh{\o}j, {Hans Christian D.} and Schwibinger, {Emil Vincent} and Ainara Nova and Troels Skrydstrup",

year = "2024",

month = jul,

doi = "10.1038/s41467-024-50083-9",

language = "English",

volume = "15",

journal = "Nature Communications",

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Unveiling the mechanism of triphos-Ru catalysed C–O bond disconnections in polymers. / Ahrens, Alexander; Batista, Gabriel Martins Ferreira; Hammershøj, Hans Christian D. et al.
In: Nature Communications, Vol. 15, 5656, 07.2024.

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

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AU - Batista, Gabriel Martins Ferreira

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AU - Schwibinger, Emil Vincent

AU - Nova, Ainara

AU - Skrydstrup, Troels

PY - 2024/7

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N2 - Ruthenium complexes with facially coordinating tripodal phosphine ligands are privileged catalysts for a broad range of (de-)hydrogenation-based transformations. Among these, C–O bond hydrogenolysis holds potential for the depolymerisation of both the biopolymer lignin and epoxy resins applied in wind turbine blades, aircrafts and more. However, this methodology is poorly understood in mechanistic terms. Here, we present a detailed investigation on the triphos-Ru catalysed C–O bond scission on a molecular level. A combination of experimental, spectroscopical and theoretical studies elucidates the reactivity of the ruthenium trimethylenemethane precatalyst, revealing the key roles of ruthenium phenolates in both catalyst activation as well as the catalytic cycle itself. Furthermore, a Ru(0)/Ru(II) oxidative addition into the C–O bond is disclosed, with a triphos-Ru(0) dihydrogen complex as entry point. With the molecular nature of the operating triphos-Ru species and the thermodynamics and kinetics of the catalysis unravelled, improvements of established methods as well as design of related transformations may become possible.

AB - Ruthenium complexes with facially coordinating tripodal phosphine ligands are privileged catalysts for a broad range of (de-)hydrogenation-based transformations. Among these, C–O bond hydrogenolysis holds potential for the depolymerisation of both the biopolymer lignin and epoxy resins applied in wind turbine blades, aircrafts and more. However, this methodology is poorly understood in mechanistic terms. Here, we present a detailed investigation on the triphos-Ru catalysed C–O bond scission on a molecular level. A combination of experimental, spectroscopical and theoretical studies elucidates the reactivity of the ruthenium trimethylenemethane precatalyst, revealing the key roles of ruthenium phenolates in both catalyst activation as well as the catalytic cycle itself. Furthermore, a Ru(0)/Ru(II) oxidative addition into the C–O bond is disclosed, with a triphos-Ru(0) dihydrogen complex as entry point. With the molecular nature of the operating triphos-Ru species and the thermodynamics and kinetics of the catalysis unravelled, improvements of established methods as well as design of related transformations may become possible.

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Unveiling the mechanism of triphos-Ru catalysed C–O bond disconnections in polymers

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