Reactivity of Cobalt Clusters Co^±/0 with Dinitrogen: Superatom Co₆⁺ and Superatomic Complex Co₅N₆

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 = 2-30) and anionic Co^- clusters (n = 7-53) which are relatively inert in reacting with nitrogen in the fast-flow tube, Co⁺ clusters readily react with nitrogen resulting in adducts of one or multiple N₂ except Co₆⁺ 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⁺ clusters with nitrogen and unveiled the open-shell superatomic stability of Co₆⁺ within a highly symmetric (D_3d) structure. The D_3d Co₆⁺ bears an electron configuration of a half-filled superatomic 1P orbital (i.e., 1S²1P³||1D⁰), a large α-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⁺ and N₂ 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 Co₅⁺ 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 Co₆⁺ with aromaticity, sheds light on special and general superatoms.