Aromatic character of planar boron-based clusters revisited by ring current calculations

[Unknown] Hung Tan Pham, Kie Zen Lim, Remco W. A. Havenith, [No Value] Minh Tho Nguyen

Research output: Contribution to journalArticleAcademicpeer-review

21 Citations (Scopus)

Abstract

The planarity of small boron-based clusters is the result of an interplay between geometry, electron delocalization, covalent bonding and stability. These compounds contain two different bonding patterns involving both sigma and pi delocalized bonds, and up to now, their aromaticity has been assigned mainly using the classical (4N + 2) electron count for both types of electrons. In the present study, we reexplored the aromatic feature of different types of planar boron-based clusters making use of the ring current approach. B3(+/-), B-4(2-), B-5(+/-), B-6, B-7(-), B-8(2-), B-9(-), B-10(2-), B-11(-), B-12, B-13(+), B-14(2-) and B-16(2-) are characterized by magnetic responses to be doubly sigma and pi aromatic species in which the pi aromaticity can be predicted using the (4N + 2) electron count. The triply aromatic character of B-12 and B-13(+) is confirmed. The pi electrons of B-18(2-), B-19(-) and B-20(2-) obey the disk aromaticity rule with an electronic configuration of [1 sigma(2)1 pi(4)1 delta(4)2 sigma(2)] rather than the (4N + 2) count. The double aromaticity feature is observed for boron hydride cycles including B@B5H5+, Li7B5H5 and M@BnHnq clusters from both the (4N + 2) rule and ring current maps. The double pi and sigma aromaticity in carbon-boron planar cycles B7C-, B8C, B6C2, B9C-, B8C2 and B7C3- is in conflict with the Huckel electron count. This is also the case for the ions B11C5+/- whose ring current indicators suggest that they belong to the class of double aromaticity, in which the pi electrons obey the disk aromaticity characteristics. In many clusters, the classical electron count cannot be applied, and the magnetic responses of the electron density expressed in terms of the ring current provide us with a more consistent criterion for determining their aromatic character.

Original languageEnglish
Pages (from-to)11919-11931
Number of pages13
JournalPPCP : Physical Chemistry Chemical Physics
Volume18
Issue number17
DOIs
Publication statusPublished - 2-May-2016

Keywords

  • MOLECULAR MAGNETIC-PROPERTIES
  • ALL-METAL
  • ELECTRONIC-STRUCTURE
  • CARBON BUCKYBALLS
  • CURRENT-DENSITY
  • FULLERENE
  • INSTABILITY
  • AL-4(2-)
  • PARTICLE
  • ORIGIN

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