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

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).

authors

• Klein, Douglas

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

published in

• Afinidad  Journal

keywords

• Carborane
• Computational Chemistry
• DFT
• Endohedral System
• Molecular Architecture
• Radical

start page

• 32

end page

• 38

volume

• 65

issue

• 533