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A bidentate Lewis acid with a telluronium ion as an anion-binding site

Nature Chemistry volume 2, pages 984–990 (2010)Cite this article

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Abstract

The search for receptors that can selectively capture small and potentially toxic anions in protic media has sparked a renewed interest in the synthesis and anion-binding properties of polydentate Lewis acids. Seeking new paradigms to enhance the anion affinities of such systems, we synthesized a bidentate Lewis acid that contains a boryl and a telluronium moiety as Lewis acidic sites. Anion-complexation studies indicate that this telluronium borane displays a high affinity for fluoride in methanol. Structural and computational studies show that the unusual fluoride affinity of this bidentate telluronium borane can be correlated with the formation of a B–F → Te chelate motif supported by a strong lone-pair(F) → σ*(Te–C) donor–acceptor interaction. These results, which illustrate the viability of heavier chalcogenium centres as anion-binding sites, allow us to introduce a novel strategy for the design of polydentate Lewis acids with enhanced anion affinities.

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Figure 1: Anion complexation by chelating cationic boranes and Lewis acidic properties of group 16 and 17 compounds.
Figure 2: Synthesis and reactivity of the chalcogenium borane salts [1]OTf and [2]OTf.
Figure 3: Crystal structures of the chalcogenium borane salts and their neutral precursors.
Figure 4: Photophysical properties of the chalcogenium boranes [1]+ and [2]+.
Figure 5: Spectroscopic evidence for the formation and structure of 1-F.
Figure 6: Structural and bonding characteristics of 1-F and 2-F.

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Acknowledgements

This work was supported by the National Science Foundation (CHE-0952912) and the Welch Foundation (A-1423).

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Authors and Affiliations

  1. Department of Chemistry, Texas A&M University, College Station, Texas, 77843-3255, USA

    Haiyan Zhao & François P. Gabbaï

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  1. Haiyan Zhao
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Contributions

H.Z. carried out all of the experimental, analytical and computational work. F.P.G. directed the project and assisted with the preparation of the manuscript.

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Correspondence to François P. Gabbaï.

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Supplementary information

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Supplementary information (PDF 1549 kb)

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Crystallographic data for compound 1 (CIF 21 kb)

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Crystallographic data for the fluoride salt of compound 1 (CIF 23 kb)

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Crystallographic data for triflate salt of compound 1 (CIF 25 kb)

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Crystallographic data for compound 2 (CIF 18 kb)

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Crystallographic data for the fluoride salt of compound 2 (CIF 22 kb)

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Crystallographic data for the triflate salt of compound 2 (CIF 24 kb)

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Zhao, H., Gabbaï, F. A bidentate Lewis acid with a telluronium ion as an anion-binding site. Nature Chem 2, 984–990 (2010). https://doi.org/10.1038/nchem.838

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