In Search of the Smallest Boroxol-Type Heterocyclic Ring System: Planar
Hexagonal B3S3+ Cluster with Double 6π/2σ Aromaticity
Abstract
Boroxol (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: 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 B3S3 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. Prior systems such as borazine, boroxine,
and boronyl boroxine only deal with π aromaticity as in benzene.