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Controlled homocatenation of boron on a transition metal

Nature Chemistry volume 4, pages 563–567 (2012)Cite this article

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Abstract

Only a handful of elements are able to be controllably homocatenated (that is, to be formed into one- or two-dimensional chains or rings of the element), because most have weak element–element bonds. Boron forms strong B–B bonds, but its favourable cluster formation makes homocatenation very difficult. Recently, the coupling of borylene (:BR) ligands on a metal was predicted computationally. We have brought this prediction to fruition experimentally, and extended it by adding two further borylene units, stepwise forming a B4 chain bound to a metal under mild conditions. This complex is a useful model for understanding the metal–boron interactions required to promote transition of the boron atoms from borylene ligands to oligoborane networks bound side-on. The concept shows great promise for the controlled construction of one-dimensional boron chains.

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Figure 1: Relevant published synthetic results and summary of the syntheses performed herein.
Figure 2: Molecular structures as derived from X-ray crystallography.
Figure 3: Results of DFT calculations on complexes 2 (left) and 4 (right).

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Acknowledgements

Financial support from the European Research Council (Advanced Investigator Grant to H.B.) is acknowledged.

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Authors and Affiliations

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

    Holger Braunschweig, Qing Ye, Alfredo Vargas, Rian D. Dewhurst, Krzysztof Radacki & Alexander Damme

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  1. Holger Braunschweig
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  2. Qing Ye
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  3. Alfredo Vargas
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  4. Rian D. Dewhurst
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  5. Krzysztof Radacki
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Contributions

H.B. conceived and supervised the study, Q.Y. performed the syntheses, A.V. performed the computational experiments and K.R. and A.D. performed the X-ray crystallographic measurements. R.D.D., Q.Y. and A.V. analysed the data and co-wrote the paper.

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Correspondence to Holger Braunschweig.

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The authors declare no competing financial interests.

Supplementary information

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Supplementary information (PDF 658 kb)

Supplementary information

Crystallographic data for compound 2. (CIF 19 kb)

Supplementary information

Crystallographic data for compound 3. (CIF 20 kb)

Supplementary information

Crystallographic data for compound 4. (CIF 31 kb)

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Braunschweig, H., Ye, Q., Vargas, A. et al. Controlled homocatenation of boron on a transition metal. Nature Chem 4, 563–567 (2012). https://doi.org/10.1038/nchem.1379

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