Carba-closo-dodecaborate Anions with Two Functional Groups: [1-R-12-HCC-closo-1-CB11H10]− (R = CN, NC, CO2H, C(O)NH2, NHC(O)H)

Disubstituted carba-closo-dodecaborate anions with one functional group bonded to the cluster carbon atom and one ethynyl group bonded to the antipodal boron atom were synthesized from easily accessible {closo-1-CB11} clusters. [Et4N]­[1-NC-12-HCC-closo-1-CB11H10] ([Et4N]4b) was prepared starting from Cs­[12-Et3SiCC-closo-1-CB11H11] (Cs1c) via salts of the anions [1-HO­(O)­C-12-HCC-closo-1-CB11H10]− (2b) and [1-H2N­(O)­C-12-HCC-closo-1-CB11H10]− (3b). In a similar reaction sequence [Et4N]­[1-CN-12-HCC-closo-1-CB11H10] ([Et4N]7b) was obtained from Cs­[1-H2N-12-HCC-closo-1-CB11H10] (Cs5b) by formamidation to yield [Et4N]­[1-H­(O)­CHN-12-HCC-closo-1-CB11H10] ([Et4N]6b) and successive dehydration. In addition, the synthesis of the isonitrile [Et4N]­[1-CN-closo-1-CB11H11] ([Et4N]7a) is presented. The {closo-1-CB11} derivatives were characterized by multinuclear NMR as well as vibrational spectroscopy, mass spectrometry, and elemental analysis. The crystal structures of [Et4N]­[1-HO­(O)­C-12-HCC-closo-1-CB11H10] ([Et4N]2b), [Et4N]­[1-H2N­(O)­C-12-HCC-closo-1-CB11H10] ([Et4N]3b), [Et4N]­[1-NC-12-HCC-closo-1-CB11H10] ([Et4N]4b), [Et4N]­[1-H­(O)­CHN-12-HCC-closo-1-CB11H10] ([Et4N]6b), [Et4N]­[1-CN-12-HCC-closo-1-CB11H10] ([Et4N]7b), and K­[1-H­(O)­CHN-closo-1-CB11H11] ([Et4N]6a) were determined. The transmission of electronic effects through the carba-closo-dodecaboron cage was studied based on 13C NMR spectroscopic data, by results derived from density functional theory calculations, and by a comparison to the data of related benzene and bicyclo[2.2.2]­octane derivatives.