Isolation and characterisation of both the first fluoroxyfluorofullerene C60F17OF and oxahomofluorofullerenol C60F17O.OH

The first fluoroxyfluorofullerene C60F17OF (A) has been isolated from the fluorination of [60]fullerene with a mixture of MnF3 and K2NiF6 at 480 °C. This compound has a shorter HPLC retention time than the isomeric fluorofullerene ethers (oxahomofullerenes) and is less stable towards EI mass spectrometry. It fragments by losing OF as a single entity and shows no formation of C60O as a fragment ion. By contrast, the ethers fragment by first losing a number of F atoms and then CO, and ultimately show also the presence of C60O, whilst epoxides lose CO as a main fragmentation step and do not give C60O. The first oxahomofluorofullerenol C60F17O.OH (B) has been isolated from the UV-irradiation of a toluene solution of C60F18 in air during 65 h and readily eliminates HF due to adjacent F and OH groups during EI mass spectrometry. The structures of both the compounds have been deduced from 1D and 2D 19F NMR spectroscopy. Just as oxygen inserts into FCCF bonds of C60F18 to give ethers, so insertion into a CF bond gives A. The oxahomofluorofullerenol B is produced by SN2′ substitution of F by OH, followed by oxygen insertion into a 6:5-bond (αβ to the OH group) giving a motif not seen previously in fluorofullerenes.