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Metal-free binding and coupling of carbon monoxide at a boron–boron triple bond

Nature Chemistry volume 5, pages 1025–1028 (2013)Cite this article

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Abstract

Many metal-containing compounds, and some metal-free compounds, will bind carbon monoxide. However, only a handful of metal-containing compounds have been shown to induce the coupling of two or more CO molecules, potentially a method for the use of CO as a one-carbon-atom building block for the synthesis of organic molecules. In this work, CO was added to a boron–boron triple bond at room temperature and atmospheric pressure, resulting in a compound into which four equivalents of CO are incorporated: a flat, bicyclic, bis(boralactone). By the controlled addition of one CO to the diboryne compound, an intermediate in the CO coupling reaction was isolated and structurally characterized. Electrochemical measurements confirm the strongly reducing nature of the diboryne compound.

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Figure 1: Selected products of published metal-mediated CO-coupling reactions.
Figure 2: Synthesis of 2 and 3 and some plausible electronic descriptions of 3.
Figure 3: Molecular structures of 2 and 3.

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Acknowledgements

This work was supported by the Deutsche Forschungsgemeinschaft (grant no. BR 1149/13-1).

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Authors and Affiliations

  1. Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, Würzburg, 97074, Germany

    Holger Braunschweig, Theresa Dellermann, Rian D. Dewhurst, William C. Ewing, Kai Hammond, J. Oscar C. Jimenez-Halla, Thomas Kramer, Ivo Krummenacher, Jan Mies, Ashwini K. Phukan & Alfredo Vargas

  2. Department of Chemistry (DCNE), Universidad de Guanajuato, Noria Alta s/n 36050, Guanajuato, Mexico

    J. Oscar C. Jimenez-Halla

  3. Department of Chemical Sciences, Tezpur University, Napaam, Assam, 784028, India

    Ashwini K. Phukan

  4. Department of Chemistry, School of Life Sciences, University of Sussex, Brighton, Sussex, BN1 9QJ, UK

    Alfredo Vargas

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  1. Holger Braunschweig
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Contributions

H.B. conceived and supervised the study. J.M., T.D., K.H. and W.C.E. performed the syntheses and spectroscopic studies. J.O.C.J.H., A.V. and A.K.P. performed the DFT computational studies. I.K. performed the EPR spectroscopic and cyclic voltammetry. T.K. performed the X-ray crystallographic measurements. R.D.D. wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Holger Braunschweig.

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Supplementary information

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Supplementary information (PDF 948 kb)

Supplementary information

Crystallographic data for compound 2. (CIF 36 kb)

Supplementary information

Crystallographic data for compound 3. (CIF 26 kb)

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Braunschweig, H., Dellermann, T., Dewhurst, R. et al. Metal-free binding and coupling of carbon monoxide at a boron–boron triple bond. Nature Chem 5, 1025–1028 (2013). https://doi.org/10.1038/nchem.1778

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