Transmission of electronic effects by icosahedral carboranes; skeletal carbon-13 chemical shifts and ultraviolet-visible spectra of substituted aryl-p-carboranes (1,12-dicarba-closo-dodecaboranes)

A series of para-carboranes (1,12-dicarba-closo-dodecaboranes) substituted at one or both carbon atoms by phenyl groups bearing a range of electron-releasing or -withdrawing substituents (X = NMe2, NH2, OH, OMe, Me, CF3 or NO2), principally at the para positions, has been prepared. The carbon-13 NMR shifts of the monoaryl compounds (4-XC6H4)CB10H10CH showed a linear increase in shielding of the unsubstituted (antipodal) cage carbon, C12, and a linear decrease at the substituted position, C1, with increasing electron-donating power of the substituent represented by its Hammett sigma(P) value. Purely inductive, sigma(I), or resonance sigma(R), parameters gave less satisfactory plots. The diaryl series of 4-nitrophenyl derivatives showed the same relationships. Calculations of electron densities showed that the C-13 NMR shifts correspond with charge density in the tangential p orbitals. The UV absorptions of the monoaryl p-carboranes have substantial red-shifts compared with the corresponding substituted benzenes, while those of the 4-nitrophenyl compounds having Lt-dimethylamino or 4-oxide anion substituents in the second phenyl group extend into the visible. The colour is attributed to changes in the nitro n --> pi* absorption rather than conjugation or intermolecular charge transfer. Two anhydrous polymorphs and a hydrate of the (18-crown-6)potassium salt of this nitrophenoxide have been identified (18-crown-6 = 1,4,7,10,13,16-hexaoxacyclooctadecane). The results establish that p-carborane transmits electronic effects, perhaps as a formally unsaturated system or possibly in a similar manner to the staffanes (bicyclo[1.1.1]pentanes) and other formally saturated hydrocarbon linkages.