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

Zhongfang Chen, Haijun Jiao, Damian Moran, Andreas Hirsch*, Walter Thiel, Paul von Ragué Schleyer

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

41 Citations (Scopus)


B3LYP/6-31G* computations predict the relative energies and stabilities of the endohedral (XΓ20H20) and exohedral (XC20H20) 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. C20H21 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.

Original languageEnglish
Pages (from-to)2075-2079
Number of pages5
JournalJournal of Physical Chemistry A
Issue number12
Publication statusPublished - 27 Mar 2003
Externally publishedYes


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