Abstract
AbstractBoroxol (B3O3) rings and relevant hexagonal B3S3 structural blocks are ubiquitous in boron oxide/sulfide glasses, crystals, and high‐temperature liquids. However, the isolation of an ultimate heterocyclic B3O3 or B3S3 cluster in the free‐standing form, with as few as six atoms, has been unsuccessful so far. We report on computational design of the simplest case of such a system: the highly symmetric D3h B3S3+ (1A1′) cluster. It is the well‐defined global minimum on the potential energy surface, following global searches and electronic structure calculations at the B3LYP and single‐point CCSD(T) levels. Chemical bonding analysis reveals an ideal system with skeleton Lewis BS σ single bonds and unique double 6π/2σ aromaticity, which underlies its stability. The cluster turns out to be an inorganic analog of the 3,5‐dehydrophenyl cation, a typical double π/σ aromatic system. It offers an example for chemical analogy between boron‐based heterocyclic clusters and aromatic hydrocarbons. Double π/σ aromaticity is also a new concept in heterocyclic boron clusters. Previous systems such as borazine, boroxine, and boronyl boroxine only deal with π aromaticity as in benzene.
Published Version
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