For the first time, the direct C(sp(2))-H functionalization methodology has successfully been applied to cause nucleophilic modification of mono- and diazine-N-oxides with the 1,2-closo-carborane moiety. As a result of these cross-coupling reactions uncatalyzed by transition metals, a series of novel C-modified heterocyclic and open-chain (vinyl acetylene) carboranes have been obtained. Complexes of phenanthrolinyl-substituted omicron-carborane with Cu(II) of various architectures have been synthesized.