The Quest for Stable Borozene Core in Main‐Group Capped Inverse Sandwich Complexes, [(HE)2B6H6]2− (E=B, Al, Ga, In, and Tl)

The ubiquitous chemistry of benzene led us to explore ways to stabilise analogous borozene, by capping them with appropriate groups. The mismatch in overlap of ring‐cap fragment molecular orbitals in [(HB)2B6H6]2− is overcome by replacing the two BH caps with higher congeners of boron. We calculated...

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Bibliographic Details
Published in:Chemistry : a European journal 2024-09, Vol.30 (54), p.e202402410-n/a
Main Authors: Joshi, Gaurav, Jemmis, Eluvathingal D.
Format: Article
Language:English
Subjects:
Aluminium
Aromaticity
Benzene
Borane
Boron
Borozene
Capping
Caps (structural)
Congeners
Hexagonal-bipyramidal
Molecular orbitals
Orbital stability
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Summary:The ubiquitous chemistry of benzene led us to explore ways to stabilise analogous borozene, by capping them with appropriate groups. The mismatch in overlap of ring‐cap fragment molecular orbitals in [(HB)2B6H6]2− is overcome by replacing the two BH caps with higher congeners of boron. We calculated the relative energies of all the polyhedral structural candidates for [(HE)2B6H6]2− (E=Al−Tl) and found hexagonal bipyramid (HBP) to be more stable with Al−H caps. A global minimum search also gives HBP as the most stable structure for [Al2B6H8]2−. The capped B6H6 ring in [(HAl)2B6H6]2− has aromaticity comparable to that of benzene. Orbital Engineering helps to design ideal caps to stabilize {B6H6} core in inverse sandwiches using group 13 elements as caps. Optimal ring‐cap overlap makes AlH and GaH as nearly ideal caps for B6H6 ring. Estimates of aromaticity of HEB6H6EH using NICS is comparable to that of benzene, justifying the borozene nomenclature.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202402410