Structures and stabilities of endo- and exohedral dodecahedrane complexes (XΓ20H20 and XC20H20, X = H+, H, N, P, C-, Si-, O+, S+)

Chen Z, Jiao H, Moran DM, Hirsch A, Thiel W, Schleyer P (2003)

Publication Type: Journal article, Original article

Publication year: 2003

Journal

Journal of Physical Chemistry A American Chemical Society

Original Authors: Chen Z., Jiao H., Moran D., Hirsch A., Thiel W., von Rague Schleyer P.

Publisher: American Chemical Society

Book Volume: 107

Pages Range: 2075-2079

Journal Issue: 12

DOI: 10.1021/jp0273631

Abstract

B3LYP/6-31G* computations predict the relative energies and stabilities of the endohedral (XΓH) and exohedral (XCH) dodecahedrane complexes (X = H, H, N, P, C, Si, O, S). H does not bind endohedrally but bridges a C-C bond exohedrally; the proton affinity is 185.3 kcal/mol. Except for O, all other guest species (H, N, P, C, Si, S) are minima at the cage center. The H-atom inclusion energy is similar to that of helium (36.3 vs 38.0 kcal/mol), whereas the other endohedral complexes have much higher inclusion energies (125-305 kcal/mol). In all cases, the endohedral complexes are energetically less favorable than their exohedral isomers. CH has a cage-ruptured structure, whereas N, P, and their isoelectronic analogues have exohedral structures and bind as doublet states to broken cage C-C bonds. Endohedral H, N, C, O, and S preserve their unencapsulated ground states, whereas P and Si interact strongly with the cage and lose their atomic ground-state character.

Authors with CRIS profile

Andreas Hirsch Lehrstuhl für Organische Chemie II Paul Schleyer Naturwissenschaftliche Fakultät

Involved external institutions

Max-Planck-Institut für Kohlenforschung (MPI KoFo) / Max Planck Institute for Coal Research DE Germany (DE)

How to cite

APA:

Chen, Z., Jiao, H., Moran, D.M., Hirsch, A., Thiel, W., & Schleyer, P. (2003). Structures and stabilities of endo- and exohedral dodecahedrane complexes (XΓ20H20 and XC20H20, X = H+, H, N, P, C-, Si-, O+, S+). Journal of Physical Chemistry A, 107(12), 2075-2079. https://dx.doi.org/10.1021/jp0273631

MLA:

Chen, Zhongfang, et al. "Structures and stabilities of endo- and exohedral dodecahedrane complexes (XΓ20H20 and XC20H20, X = H+, H, N, P, C-, Si-, O+, S+)." Journal of Physical Chemistry A 107.12 (2003): 2075-2079.

BibTeX: Download