Affiliation:
1. Department of Chemistry and Biotechnology, Graduate School of Engineering, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, 113-8656, Japan.
Abstract
Nucleophilic, anionic boryl compounds are long-sought but elusive species. We report that reductive cleavage of the boron-bromine bond in
N,N
′-bis(2,6-diisopropylphenyl)-2-bromo-2,3-dihydro-1
H
-1,3,2-diazaborole by lithium naphthalenide afforded the corresponding boryllithium, which is isoelectronic with an
N
-heterocyclic carbene. The structure of the boryllithium determined by x-ray crystallography was consistent with sp
2
boron hybridization and revealed a boron-lithium bond length of 2.291 ± 0.006 angstroms. The structural similarity between this compound and the calculated free boryl anion suggests that the boron atom has an anionic charge. The
11
B nuclear magnetic resonance spectrum also supports the boryl anion character. Moreover, the compound behaves as an efficient base and nucleophile in its reactions with electrophiles such as water, methyl trifluoromethanesulfonate, 1-chlorobutane, and benzaldehyde.
Publisher
American Association for the Advancement of Science (AAAS)
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