FULLERENE DERIVATIVES: STRUCTURES AND STABILITIES OF C60O AND C70O

Abstract

Semi-empirical (MNDO) and ab-initio Hartree-Fock (3–21G) calculations on the structures and stabilities of C 60 O and C 70 O are reported. Two low energy isomers of C 60 O , formed by an oxygen atom bridging the two different C–C bonds in C 60, have been found. The first isomer has an epoxide structure with a bridging oxygen across the bond between two fused six-membered rings in C 60 (bridging C–C≈1.6 Å). Its 13 C NMR and infrared spectra are consistent with those seen for the experimentally isolated form of C 60 O . However, the second isomer containing a bridging oxygen across the bond between a five- and a six-membered ring is slightly more stable and appears to be the ground state of C 60 O . The bridging C–C bond opens out to a distance of ≈2.1 Å in this isomer. Endohedral isomers of C 60 O are calculated to be very high in energy. For C 70 O , we have characterized eight isomers formed by an oxygen atom bridging each of the eight distinct C–C bonds in C 70. The ground state isomer corresponds to oxygen bridging across an equatorial C–C bond in C 70 which opens out to a distance of ≈2.2 Å. This structure is different from the bridged paracyclene-like isomer proposed previously for C 70 O . Comparison is made between C 60 O and C 70 O .