CBe2H5−: Unprecedented 2σ/2π Double Aromaticity and Dynamic Structural Fluxionality in a Planar Tetracoordinate Carbon Cluster

Abstract

AbstractA 14‐electron ternary anionic CBe2H5− cluster containing a planar tetracoordinate carbon (ptC) atom is designed herein. Remarkably, it can be stabilized by only two beryllium atoms with both π‐acceptor/σ‐donor properties and two hydrogen atoms, which means that the conversion from planar methane (transition state) to ptC species (global minimum) requires the substitution of only two hydrogen atoms. Moreover, two ligand H atoms exhibit alternate rotation, giving rise to interesting dynamic fluxionality in this cluster. The electronic structure analysis reveals the flexible bonding positions of ligand H atoms due to C−H localized bonds, highlighting the rotational fluxionality in the cluster, and two CBe2 3c–2e delocalized bonds endow its rare 2σ/2π double aromaticity. Unprecedentedly, the fluxional process exhibits a conversion in the type of bonding (σ bond↔π bond), which is an uncommon fluxional mechanism. The cluster can be seen as an attempt to apply planar hypercoordinate carbon species to molecular motors.