Chemical reactions that break, or activate, C-H and C-F are of tremendous synthetic interest. The intramolecular C-F bond activation of a tungsten carbonyl system has been studied by time-resolved infrared spectroscopy. The formation of solvent complexes and the final product are monitored using time-resolved infrared spectroscopy of the CO stretches. The rate of the reaction is shown to be limited by the formation of an intermolecular complex between the tungsten metal center and a solvent molecule. Comparison with DFT calculations shows that in the absence of solvent molecules the intramolecular complex with the tethered perfluorobenzene ring is energetically favorable, but is not the primary kinetic product because of the initial geometry of the complex.