Theoretical study of new L-(N₅⁺)-L species with a small inorganic donor ligand L

We perform a computational mapping study of a family of new inorganic species, based on idea of donor–acceptor type bonding between N⁺ and a ligand L with a terminal electron lone pair. The nitrogen ion is seen as being in an atomic ¹D state, with empty 2p acceptor orbitals [I.S.K. Kerkines., A. Papakondylis, A. Mavridis, J. Phys. Chem. A, 2002, 106, 4435]. We consider a series of small ligands, such as PN, CCH^-, CCCN^-, NH2^-, and others. Chemical bonding analysis confirms the suggested bonding picture as characteristic for experimentally known N₅⁺ and N(CO)₂⁺ as well as for most of the predicted species. A number of these new compounds is found to be thermodynamically stable with respect to the existing N₅⁺ or N(CN)₂^-. They are candidates for new synthetic targets.