1-H2N-CB11F11]---synthesis and reactions of a functionalized fluorinated carbadodecaborate anion

In anhydrous hydrogen fluoride, K1-H2N-CB11H11] is fluorinated with elemental fluorine to produce K1-H2N-CB11F11]. Under strong alkaline conditions, two fluorine atoms of the 1-H2N-CB11F11]- anion are regioselectively exchanged, yielding the 1-H2N-4,6-(HO)2-CB11F9]- anion via 1-H2N-6-HO-CB11F10]- as an intermediate. Both hydroxycarborate anions were isolated as Ph4P]+ salts. All of the species were characterized by IR, Raman, and multi-NMR spectroscopy, thermal analysis (DSC) as well as by mass spectrometry (MALDI). The assignment of the NMR signals was supported by DFT calculations. Solid-state structures of K1-H2N-CB11F11], BzPh3P]1-H2N-CB11F11], Ph4P]1-H2N-4,6-(HO)2-CB11F9], Ph4P]1-H2N-6-HO-CB11F10], and BzPh3P]1-H2N-CB11H11] were determined by single-crystal X-ray diffraction.