We report a joint experimental and theoretical study on the reactions of cobalt clusters (Co-n(+/-/0 )) with nitrogen using the customized reflection time-of-flight mass spectrometer combined with a 177.3 nm deep-ultraviolet laser. Comparing to the behaviors of neutral Co-n (n = 2-30) and anionic Co-n- clusters (n = 7-53) which are relatively inert in reacting with nitrogen in the fast-flow tube, Co-n(+) clusters readily react with nitrogen resulting in adducts of one or multiple N-2 except Co-6(+) which stands firm in the reaction with nitrogen. Detailed quantum chemistry calculations, including the energetics, electron occupancy, and orbital analysis, well-explained the reasonable reactivity of Co-n(+) clusters with nitrogen and unveiled the open-shell superatomic stability of Co-6(+) within a highly symmetric (D-3d) structure. The D-3d Co-6(+) bears an electron configuration of a half-filled superatomic 1P orbital (i.e., 1S(2)1P(3)parallel to 1D(0)), a large alpha-highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap, symmetric multicenter bonds, and reasonable electron delocalization pertaining to metallic aromaticity. Topology analysis by atom-in-molecule illustrates the interactions between Co(n)(+)( )and N-2 corresponding to covalent bonds, but the Co-N interactions in cationic Co2+N2 and Co6+N2 clusters are apparently weaker than those in the other systems. In addition, we identify a superatomic complex Co5N6+ which exhibits similar frontier orbitals as the naked Co-5(+) cluster, but the alpha HOMO-LUMO gap is nearly double-magnified, which is consistent with the high-abundance peak of Co5N6+ in the experimental observation. The enhanced stability of such a ligand-coordinated superatomic complex Co5N6+, along with the superatom Co-6(+) with aromaticity, sheds light on special and general superatoms.