Aromatization of Fulvene by Complexation with Lithium

At the B3LYP/6-311++G(d,p) level, approach of a lithium atom to a face of the fulvene molecule leads to formation of a complex with binding energy 41 kcal/mol and significant ion-pair character. The fulvene moiety gains a delocalized aromatic cyclic π system, documented by the geometry-based aromaticity index HOMA, and a strong diatropic ring current, visualized by ipsocentric calculation of the π current-density, which leads to an “aromatic” NICS value of −11 ppm.