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Approaching Dianionic Tetraoxadiborecine Macrocycles: 10-Membered Bora-Crown Ethers Incorporating Borafluorenate Units

The addition of non-benzenoid quinones, acenapthenequinone or aceanthrenequinone, to the 9-carbene-9-borafluorene monoanion ( 1 ) affords the first examples of dianionic 10-membered bora-crown ethers ( 2 – 5 ), which are characterized by multi-nuclear NMR spectroscopy (¹H, ¹³C, ¹¹B), X-ray crystallography, elemental analysis, and UV/Vis spectroscopy. These tetraoxadiborecines have distinct absorption profiles based on the positioning of the alkali metal cations. When compound 4 , which has a vacant C₄B₂O₄ cavity, is reacted with sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, a color change from purple to orange serves as a visual indicator of metal binding to the central ring, whereby the Na⁺ ion coordinates to four oxygen atoms. A detailed theoretical analysis of the calculated reaction energetics is provided to gain insight into the reaction mechanism for the formation of 2 – 5 . These data, and the electronic structures of proposed intermediates, indicate that the reaction proceeds via a boron enolate intermediate.