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In Search of the Smallest Boroxol-Type Heterocyclic Ring System: Planar Hexagonal B3S3+ Cluster with Double 6π/2σ Aromaticity
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  • Lijuan Zhang,
  • Linyan Feng,
  • he bian,
  • Ling Pei,
  • Dazhi Li,
  • Huajin Zhai
Lijuan Zhang
Binzhou University
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Linyan Feng
Shanxi University
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he bian
Binzhou University
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Ling Pei
Binzhou University
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Dazhi Li
Binzhou University
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Huajin Zhai
Shanxi University
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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.

Peer review status:ACCEPTED

01 Feb 2020Submitted to International Journal of Quantum Chemistry
04 Feb 2020Submission Checks Completed
04 Feb 2020Assigned to Editor
04 Feb 2020Reviewer(s) Assigned
26 Feb 2020Review(s) Completed, Editorial Evaluation Pending
28 Feb 2020Editorial Decision: Revise Minor
03 Mar 20201st Revision Received
03 Mar 2020Submission Checks Completed
03 Mar 2020Assigned to Editor
06 Mar 2020Reviewer(s) Assigned
13 Mar 2020Review(s) Completed, Editorial Evaluation Pending
13 Mar 2020Editorial Decision: Accept