title: Can aromaticity coexist with diradical character? An ab initio valence bond study of S2N2 and related 6π-electron four-membered rings E2N2 and E4(2+) (E=S, Se, Te).
abstract: A series of 6π-electron 4-center species, E(2)N(2) and E(4)(2+) (E=S, Se, Te) is studied by means of ab initio valence bond methods with the aims of settling some controversies on 1) the diradical character of these molecules and 2) the radical sites, E or N, of the preferred diradical structure. It was found that for all molecules, the cumulated weights of the two possible diradical structures are always important and close to 50 %, making these molecules comparable to ozone in terms of diradical character. While the two diradical structures are degenerate in the E(4)(2+) dications, they have on the contrary strongly unequal weights in the E(2)N(2) neutral molecules. In these three molecules, the electronic structure is dominated by one diradical structure, in which the radical sites are the two nitrogen atoms, while the other diradical structure is much less important. The ordering of the various VB structures in terms of their calculated weights is confirmed by the relative energies of individual VB structures. In all cases, the major diradical structure (or both diradical structures when they are degenerate) is (are) the lowest one(s), while the covalent VB structures lie higher in energy. The vertical resonance energies are considerable in S(2)N(2) and S(4)(2+), about 80 % of the estimated value for benzene, and diminish as one goes down the periodic table (S→Se→Te). This confirms the aromatic character of these species, as already demonstrated for S(2)N(2) on the basis of magnetic criteria. This and the high weights and stabilities of one or both diradical structures in all systems indicates that aromaticity and diradical character do not exclude each other, contrary to what is usually claimed. Furthermore, it is shown that the diradical structures find their place in a collective electron flow responsible for the ring currents in the π system of these species.
authors.affiliation: Laboratoire de Chimie Théorique, UPMC Université Paris 06, CNRS UMR 7616, Paris, France. braida@lct.jussieu.fr
authors.forename: Benoît
authors.initials: B
authors.lastname: Braïda
authors.forename: Aurélien
authors.initials: A
authors.lastname: Lo
authors.forename: Philippe C
authors.initials: PC
authors.lastname: Hiberty