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Efficient hydrogenation of organic carbonates, carbamates and formates indicates alternative routes to methanol based on CO2 and CO

Nature Chemistry volume 3, pages 609–614 (2011)Cite this article

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Abstract

Catalytic hydrogenation of organic carbonates, carbamates and formates is of significant interest both conceptually and practically, because these compounds can be produced from CO2 and CO, and their mild hydrogenation can provide alternative, mild approaches to the indirect hydrogenation of CO2 and CO to methanol, an important fuel and synthetic building block. Here, we report for the first time catalytic hydrogenation of organic carbonates to alcohols, and carbamates to alcohols and amines. Unprecedented homogeneously catalysed hydrogenation of organic formates to methanol has also been accomplished. The reactions are efficiently catalysed by dearomatized PNN Ru(II) pincer complexes derived from pyridine- and bipyridine-based tridentate ligands. These atom-economical reactions proceed under neutral, homogeneous conditions, at mild temperatures and under mild hydrogen pressures, and can operate in the absence of solvent with no generation of waste, representing the ultimate ‘green’ reactions. A possible mechanism involves metal–ligand cooperation by aromatization–dearomatization of the heteroaromatic pincer core.

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Figure 1: Alternative routes to methanol based on methyl formate, dimethyl carbonate and organo-carbamates.
Figure 2: Hydrogenation of a benzyl carbamate.
Figure 3: X-ray structure of complex 3 (50% probability level).
Figure 4: Reactivities of the saturated Ru(II)–trans-dihydride complex 3, suggesting its intermediacy in the catalytic hydrogenation mechanism.
Figure 5: Postulated mechanism for novel, homogeneous hydrogenation of dimethyl carbonate and methyl formate to methanol catalysed by complex 1.

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Acknowledgements

This research was supported by the European Research Council under the FP7 framework (ERC no. 246837), by the Israel Science Foundation, and by the MINERVA Foundation. D.M. is the Israel Matz Professorial Chair of Organic Chemistry.

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Authors and Affiliations

  1. Department of Organic Chemistry, The Weizmann Institute of Science, Rehovot, 76100, Israel,

    Ekambaram Balaraman, Chidambaram Gunanathan, Jing Zhang & David Milstein

  2. Department of Chemical Research Support, The Weizmann Institute of Science, Rehovot, 76100, Israel,

    Linda J. W. Shimon

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  1. Ekambaram Balaraman
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Contributions

E.B. carried out catalytic experiments, mechanistic studies and contributed to writing the manuscript. C.G. carried out catalytic experiments and contributed to writing the manuscript. J.Z. prepared and crystallized complex 3. L.J.W.S. conducted the X-ray structural study of complex 3. D.M. carried out the design and direction of the project and contributed to writing the manuscript.

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Correspondence to David Milstein.

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Crystallographic data for compound 3 (CIF 19 kb)

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Balaraman, E., Gunanathan, C., Zhang, J. et al. Efficient hydrogenation of organic carbonates, carbamates and formates indicates alternative routes to methanol based on CO2 and CO. Nature Chem 3, 609–614 (2011). https://doi.org/10.1038/nchem.1089

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