Fullerene-like chemistry at the interior carbon atoms of an alkene-centered C26H12 geodesic polyarene.
The title compound (1) undergoes 1,2-addition reactions of both electrophilic and nucleophilic reagents preferentially at the "interior" carbon atoms of the central 6:6-bond to give fullerene-type adducts 2, 3, 4, and 5. Such fullerene-like chemistry is unprecedented for a topologically 2-dimensional polycyclic aromatic hydrocarbon and qualifies this geodesic polyarene as a "bridge" between the old flat world of polycyclic aromatic hydrocarbons (PAHs) and the new round world of fullerenes. The relief of pyramidalization strain, as in the addition reactions of fullerenes, presumably contributes to the atypical mode of reactivity seen in 1. Molecular orbital calculations, however, reveal features of the nonalternant pi system in 1 that may also play an important role. Thus, the fullerene-like chemistry of 1 may be driven by two or more factors, the relative importances of which are difficult to discern.
Bronstein
Hindy E
HE
Department of Natural Science, Fordham University, 113 West 60th Street, LL 817-F, New York, New York 10023, USA. hbronstein@fordham.edu
Scott
Lawrence T
LT
D000475:Alkenes / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003500:Cyclization; D037741:Fullerenes / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009993:Osmium Tetroxide / Q000737:chemistry; D011084:Polycyclic Aromatic Hydrocarbons / Q000737:chemistry*; D013237:Stereoisomerism
D000475:Alkenes; D037741:Fullerenes; D011084:Polycyclic Aromatic Hydrocarbons; D002244:Carbon; D009993:Osmium Tetroxide