Quantification of the (anti)aromaticity of fulvalenes subjected to pi-electron cross-delocalization

摘要

[GRAPHICS] Fulvalenes 3-12 were theoretically studied at the ab initio level of theory. For the global minima structures, the occupation of the bonding pi(C=C) orbital of the interring, C=C double bond obtained by NBO analysis quantitatively proves pi-electron cross-delocalization resulting in, at least partially, 2- or 6 pi-electron aromaticity and 8 pi-electron antiaromaticity for appropriate moieties. The cross-conjugation was quantified by the corresponding occupation numbers and lengths of the interring C=C double bonds, while the aromaticity or antiaromaticity due to cross-delocalization of the pi-electrons was visualized and quantified by through-space NMR shielding surfaces.