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A two-coordinate boron cation featuring C–B+–C bonding

Nature Chemistry volume 6, pages 498–503 (2014)Cite this article

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Abstract

Two-coordinate boron cations (R2B+), referred to as borinium ions, are chemical species in which the boron bears only four valence electrons, and that are isoelectronic with hypothetical carbon dications (R2C2+). Although lone-pair-donating substituents such as amino groups have enabled the isolation of several borinium ions, diarylated and dialkylated borinium derivatives remain entirely unexplored. Here, we present the synthesis, structure and reactivity of the dimesitylborinium ion, which displays unexpectedly high thermal stability. X-ray crystallography and 11B NMR spectroscopy, supported by density functional theory calculations, reveal that the borinium ion adopts a linear two-coordinate structure in both the solid state and in solution. The boron centre is stabilized by pπ bonding from the mesityl groups and is free from coordination by the counterion or solvent molecules. This diarylborinium ion possesses exceptional Lewis acidity, accepting a pair of electrons from CO2 to cause an unusual deoxygenation reaction.

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Figure 1: Schematic representations of chemical compounds.
Figure 2: Crystal structures of 1a and 1b (50% probability ellipsoids).
Figure 3: DFT calculation of Mes2B+ at the M06-2X/6-31+G(d) level.
Figure 4: Energy diagram of the arylation–deoxygenation of CO2 with Mes2B+ to form MesC≡O+ at the PCM(o-dichlorobenzene)-M06-2X/6-311+G(d,p)//M06-2X/6-31+G(d) level.

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Acknowledgements

This work was supported by KAKENHI (22750046). The authors thank C.A. Reed for his instruction regarding carboranes synthesis and valuable discussions. RIKEN Integrated Cluster of Clusters (RICC) provided the computer resources for the DFT calculations.

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Authors and Affiliations

  1. Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, 226-8503, Yokohama, Japan

    Yoshiaki Shoji, Naoki Tanaka & Takanori Fukushima

  2. Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, 113-0033, Tokyo, Japan

    Koichiro Mikami & Masanobu Uchiyama

  3. Advanced Elements Chemistry Research Team, RIKEN Centre for Sustainable Resource Science (CSRS) and Elements Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako, 351-0198, Saitama, Japan

    Masanobu Uchiyama

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  1. Yoshiaki Shoji
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Contributions

Y.S. and T.F. conceived and designed the work. Y.S. and N.T. performed the experiments. Y.S., N.T. and T.F. analysed the experimental data. K.M. and M.U. performed the DFT calculations and analysed the computational data. Y.S., M.U. and T.F. co-wrote the paper.

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Correspondence to Yoshiaki Shoji.

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Supplementary information

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Crystallographic data for compound 1a (CIF 57 kb)

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Crystallographic data for compound 1b (CIF 18 kb)

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rystallographic data for compound 2a (CIF 49 kb)

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Shoji, Y., Tanaka, N., Mikami, K. et al. A two-coordinate boron cation featuring C–B+–C bonding. Nature Chem 6, 498–503 (2014). https://doi.org/10.1038/nchem.1948

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