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Boryl Anions

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Synthesis and Application of Organoboron Compounds

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 49))

Abstract

This chapter focuses on the chemistry of boryl anions. The first section gives a brief history of boryl anion before the first isolated boryl anion equivalent, boryllithium, emerged. Synthesis and properties of all existing boryl anions are summarized in the second section. In the third section, examples of boryl–transition metal complexes synthesized from boryl anion reagents are presented. The following fourth section describes chemistry of boryl-substituted main group element compounds made from boryl anions. At the end of this chapter, the authors provide a summary and their perspective for related fields.

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Notes

  1. 1.

    Recently, Bertrand developed the deprotonation methodology to generate base-stabilized boryl anion 33 by using three strong π-acceptor ligands on the boron center (see the previous section).

  2. 2.

    Optimized B2H6 molecule at B3LYP/6-31 + G* was used as a reference (δB 16.6 ppm) for the 11B NMR chemical shift (GIAO/B3LYP/6-311++G**). Chemical shift for B2H6 in gas phase was reported in the reference [38].

  3. 3.

    A structure with one THF molecule, opt-36 · (THF)1, could not be optimized to the minimum. A four-membered bridging structure consists of –(Li–B)2–, which corresponds to –(Li–C)2– structure observed for alkyllithium species is less probable because of the bulky substituents on the boron center.

  4. 4.

    Two carbyl(halo)cuprates, [Li(12-c-4)2][Cu(Br)CH(SiMe3)3] [59] and (Et2O)2Li[ICuC6H3-2,6-(2,4,6-(i-Pr)3C6H2)2] [60], were reported to have linear C–Cu–X–Li structure, being similar to that of 67.

  5. 5.

    In contrast to 68, a related tetranuclear copper complex possessing two aryl groups and two bromides has been structurally characterized where two bridging bromide shared one copper atom of Cu4 core [61].

  6. 6.

    For the previously reported examples for multinuclear transition metal complexes having a bridging boryl ligand, see [62–64].

  7. 7.

    The Zn-(μ2-Br) bonds [2.504 Å (av.)] in 69 were longer than those in 70 [2.4217 Å (av.)], probably due to the coordination of THF molecules toward zinc atom in 69.

  8. 8.

    See [99] for the first example of boryl complex synthesized by a salt elimination and see [100] for the first structurally characterized boryl complex made by a salt elimination.

  9. 9.

    See [101] for the first example of boryl complex synthesized by oxidative addition and see [102] for the first structurally characterized boryl complex made by oxidative addition.

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Acknowledgment

The authors acknowledge all the students, postdocs, and colleagues in our papers in the reference section, all friends whom we have discussed this chemistry, and all those who have provided funding resource.

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  1. Department of Applied Chemistry, Chuo University, 1-13-27 Kasuga, Bunkyo-ku, Tokyo, 112-8551, Japan

    Makoto Yamashita

  2. Department of Chemistry and Biotechnology, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-8656, Japan

    Kyoko Nozaki

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  1. Universitat Rovira i Virgili Directora TECAT, Tarragona, Spain

    Elena Fernández

  2. Department of Chemistry, Centre for Sustainable Chemical Processes, Durham, United Kingdom

    Andrew Whiting

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Yamashita, M., Nozaki, K. (2015). Boryl Anions. In: Fernández, E., Whiting, A. (eds) Synthesis and Application of Organoboron Compounds. Topics in Organometallic Chemistry, vol 49. Springer, Cham. https://doi.org/10.1007/978-3-319-13054-5_1

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