On the effect of radical character, substitution and atom encapsulation on the volume of icosahedral (car)boranes Academic Article uri icon

abstract

  • By means of quantum-mechanical calculations, we study the influence of the charge, spin, substituents, and atom encapsulation on the volume of the cages in icosahedral boranes and carboranes B12H122-, CB11H12-, o-C2B10H 12, m-C2B10H12, p-C 2B10H12 and 1,2-disubstituted o-C 2B10H12. Monoradicals derived from hydrogen abstraction in o-C2B10H12, m-C 2B10H12, p-C2B10H 12 lead to slight cage contractions (IΔVI < 0.1 Å3). On the other hand, 1,2-disubstitution in o-C 2B10H12 and their dianions derived from double proton abstraction on the susbtituent, and {Li*, Be 2+} atom encapsulation in B12H122-, CB11H12-, o-C2B10H 12, m-C2B10H12, p-C 2B10H12 always leads to a cage expansion, to a larger extent for endohedral compounds (ΔV ≈ 2 Å3) as compared to dianions derived from 1,2-disubstituted o-C2B 10H12 (ΔV ≈ 1 Å3) and 1,2-disubstituted o-C2B10H12 (ΔV < 0.14 Å3).

published proceedings

  • AFINIDAD

author list (cited authors)

  • Burgos, J. I., Serrano-Andres, L., Oliva, J. M., & Klein, D. J.

complete list of authors

  • Burgos, Jose I||Serrano-Andres, Luis||Oliva, Josep M||Klein, Douglas J

publication date

  • January 2008