Planar Tricyclic B8O8 and B8O8- Clusters: Boron Oxide Analogues of s-Indacene C12H8.
J Phys Chem A
; 122(8): 2297-2306, 2018 Mar 01.
Article
en En
| MEDLINE
| ID: mdl-29401396
ABSTRACT
Boron clusters and their oxides are electron-deficient species with (π and σ) aromaticity and antiaromaticity, enabling a structural and bonding analogy between them and the aromatic hydrocarbons. s-Indacene C12H8 is normally considered as a border system between the classes of aromatic and antiaromatic hydrocarbons. We show herein, via computer global-minimum searches and B3LYP and single-point CCSD(T) calculations, that boron oxide clusters D2h B8O8 (1, 1Ag) and D2h B8O8- (2, 2B2g) adopt planar tricyclic structures, which feature fused heterocyclic B3O2/B4O2/B3O2 rings and two boronyl (BO) terminals, a structural pattern analogous to the C5/C6/C5 rings in s-indacene. Bonding analyses indicate that B8O8 (1) is a formally antiaromatic 12π system, the molecular orbitals of which are largely similar to those of s-indacene. Infrared and ultraviolet-visible spectra of B8O8 (1) neutral, as well as the photoelectron spectrum of B8O8- (2) anion, are predicted computationally. The latter spectrum shows a sizable energy gap of 3.5 eV for 2, demonstrating the electronic robustness of 1. Our bonding analyses also shed critical light on the nature of bonding in s-indacene.
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Banco de datos:
MEDLINE
Idioma:
En
Revista:
J Phys Chem A
Asunto de la revista:
QUIMICA
Año:
2018
Tipo del documento:
Article
País de afiliación:
China