Relativistic calculations of aminotroponiminate complexes containing group 15 (P, As, Sb, Bi) elements

Abstract

Abstract The relativistic electronic structure calculations of N,N′-chelated pnictogenium cations containing aminotroponiminate units, (E = P(1), As(2), Sb(3), Bi(4)), have been investigated employing density functional (DF) methods, including spin–orbit relativistic corrections, via the two-component zeroth order regular approximation (ZORA) Hamiltonian. The role of replacement of the pnictogen atom when going down into the 15 group was discussed on the basis of geometrical parameters, Hirshfield charge analyses, DF reactivity indexes. The degree of electronic delocalization into the five- and seven membered rings was estimated via the electron localization function (ELF) and the nuclear independent chemical shifts (NICS) indexes. Our results show an existence of a lack of systems 2–4 to act as donor ligands for the metal complexation, compared with 1, due to the positive charge over the pnictogen atoms besides the lone-pair orbital of the pnictogen atom which lies at low energies from their corresponding reacting HOMO’s. It is also interesting to note some effects over the aromaticity when going down into the 15 group, i.e., the C5 ring is affected by the change of the pnictogen atom, while the aromaticity on the C7 ring is not affected, as suggested by the analysis of the ELF, NICS and geometrical parameters.