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A homogeneous transition metal complex for clean hydrogen production from methanol–water mixtures

Nature Chemistry volume 5, pages 342–347 (2013)Cite this article

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Abstract

The development of an efficient catalytic process that mimics the enzymatic function of alcohol dehydrogenase is critical for using biomass alcohols for both the production of H2 as a chemical energy carrier and fine chemicals under waste-free conditions. Dehydrogenation of alcohol–water mixtures into their corresponding acids with molecular hydrogen as the sole by-product from the reaction can be catalysed by a ruthenium complex with a chelating bis(olefin) diazadiene ligand. This complex, [K(dme)2][Ru(H)(trop2dad)], stores up to two equivalents of hydrogen intramolecularly, and catalyses the production of H2 from alcohols in the presence of water and a base under homogeneous conditions. The conversion of a MeOH–H2O mixture proceeds selectively to CO2/H2 gas formation under neutral conditions, thereby allowing the use of the entire hydrogen content (12% by weight). Isolation and characterization of the ruthenium complexes from these reactions suggested a mechanistic scenario in which the trop2dad ligand behaves as a chemically ‘non-innocent’ co-operative ligand.

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Figure 1: Metal–ligand co-operativity for hydrogen splitting and evolution.
Figure 2: Redox-active or chemically active metal–diazadiene–olefin combination.
Figure 3: Preparation and reactivity of [K(dme)2][Ru(H)(trop2dad)].
Figure 4: X-ray crystal structures (ORTEP) of catalyst 3 and key intermediates 5 and 6.
Figure 5: Stoichiometric reactions with 3 leading to key intermediates 4, 4′, 5, 5-D and 6 in alcohol dehydrogenation reactions.
Figure 6: Proposed simplified mechanism for the catalytic conversion of alcohols to carboxylic acids promoted by [Ru(II)(trop2dad)] and [Ru(0)(tropdae)] complexes.

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Acknowledgements

This work was supported by the Schweizer Nationalfonds (SNF), Eidgenössische Hochschule Zürich and the joint SNF/Deutsche Forschungsgemeinschaft research project ‘Unconventional Approaches to the Activation of Dihydrogen’ (FOR1175). H.G. thanks P. Edwards (University of Oxford) and Lotus Cars, in particular, for inspiration.

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Authors and Affiliations

  1. Department of Chemistry and Applied Biosciences, ETH Zürich, 8093 Zürich, Switzerland

    Rafael E. Rodríguez-Lugo, Mónica Trincado, Matthias Vogt, Friederike Tewes, Gustavo Santiso-Quinones & Hansjörg Grützmacher

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  1. Rafael E. Rodríguez-Lugo
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Contributions

G.S-Q. performed the X-ray diffraction measurements with single crystals. All other authors planned and performed the experiments. R.E.R-L., M.T. and H.G. wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Mónica Trincado or Hansjörg Grützmacher.

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The authors declare no competing financial interests.

Supplementary information

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Crystallographic data for compound 2 (CIF 28 kb)

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Crystallographic data for compound 3 (CIF 26 kb)

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Crystallographic data for compound 5 (CIF 15 kb)

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Crystallographic data for compound 6 (CIF 28 kb)

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Crystallographic data for compound 7 (CIF 28 kb)

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Rodríguez-Lugo, R., Trincado, M., Vogt, M. et al. A homogeneous transition metal complex for clean hydrogen production from methanol–water mixtures. Nature Chem 5, 342–347 (2013). https://doi.org/10.1038/nchem.1595

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