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

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.

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