STRUCTURE AND STABILITY OF MONOCYCLIC $({\rm CH})_{4-n} ({\rm BL})_{n}^{2-}$(L = CO, N2, CS) DIANIONS AND THEIR DILITHIUM COMPLEXES

Abstract

Structure and stability of monocyclic [Formula: see text] dianions ( L = CO , N 2, CS ) with 6π-electrons, which are isolobal with cyclobutadiene dianion [Formula: see text], have been investigated at the B3LYP and CCSD(T) levels of theory. ( CH )3( BL )2- have non-planar singlet ground states. [Formula: see text] have planar singlet ground states, while [Formula: see text] isomers have folded four-membered central rings. Both [Formula: see text] and [Formula: see text] have planar ground states, the ground state of [Formula: see text] has a six-membered ring with two bridging and one terminal CS. Both [Formula: see text] and [Formula: see text] have reduced aromaticity compared to [Formula: see text] as indicated by the less negative nucleus independent chemical shifts (NICS) values. The mono-, di- and trisubstituted ( CH )3( BL )2-, [Formula: see text], and [Formula: see text] also have reduced aromaticity, while the 1,3-substituted [Formula: see text] have positive NICS values due to the localization of the negative charge at the ring carbon centers. In addition, the electrostatic stabilization of Li + in favor of the singlet or triplet states depends on the nature of their structures.