Ambiphilic reactivity is a fascinating topic in chemical reactions, attracting considerable interest because ambiphilic reagents can display properties of both nucleophilicity and electrophilicity. However, most of the previous attention has been focused on the characterization of the ambiphilic reactivity, whereas the origin is less understood. Here we carry out thorough density functional theory (DFT) calculations to probe the origin of the ambiphilic reactivity of the carbyne atom in osmapentalynes, observed previously in experiment.
J. Organomet. Chem.
Aromaticity, one of the central topics in chemistry, has attracted continuing interest of both experimentalists and theoreticians.
Density functional theory (DFT) calculations were performed to examine the substituent effects on the interconversion of silabenzenes and their monocyclic non-aromatic isomers. A previous study suggested that aromaticity is the driving force for this process. Interestingly, our systematic calculations reveal that the contribution from aromaticity can be evaluated quantitatively (ca. 30 kcal mol-1). Thus it is the interplay of aromaticity and Bent's rule that determine their relative stabilities.