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.