Selective formation of C60F18(g) and C60F36(g) by reaction of [60]fullerene with molecular fluorine

Fluorination of C60(s), C60(s)–MnF2(s), C60(s)–NiF2(s) and C60(s)–MnF3(s) mixtures has been studied by Knudsen cell mass spectrometry with admission of molecular fluorine. The fluorination is selective when fullerene reacts with the fluorine chemisorbed on the MnF2 surface. When the MnF2 content in the initial mixture is at least 90 mol% both C60F18 and C60F36 are selectively formed. Under certain conditions, mixtures predominantly containing one of three compounds C60F38, C60F40, and C60F42 can be obtained. A consecutive change of the main fluorination products (C60F18 and C60F36) takes place at constant temperature (720 K) and on fluorine admission. A quantitative explanation of this fact is given. Selective fluorination of C60(s) by molecular fluorine is compared with solid-phase fluorination using MnF3(s) as a fluorinating agent.