The net reaction of monomeric Cp'(2)CeH [Cp' = 1,3,4-(Me(3)C)(3)(C(5)H(2))] in C(6)D(6) with C(6)F(6) is Cp'(2)CeF, H(2), and tetrafluorobenzyne. The pentafluorophenylmetallocene, Cp'(2)Ce(C(6)F(5)), is formed as an intermediate that decomposes slowly to Cp'(2)CeF and C(6)F(4) (tetrafluorobenzyne), and the latter is trapped by the solvent C(6)D(6) as a [2+4] cycloadduct. In C(6)F(5)H, the final products are also Cp'(2)CeF and H(2), which are formed from the intermediates Cp'(2)Ce(C(6)F(5)) and Cp'(2)Ce(2,3,5,6-C(6)F(4)H) and from an unidentified metallocene of cerium and the [2+4] cycloadducts of tetra- and trifluorobenzyne with C(6)D(6). The hydride, fluoride, and pentafluorophenylmetallocenes are isolated and characterized by X-ray crystallography. DFT(B3PW91) calculations have been used to explore the pathways leading to the observed products of the exergonic reactions. A key step is a H/F exchange reaction which transforms C(6)F(6) and the cerium hydride into C(6)F(5)H and Cp'(2)CeF. This reaction starts by an eta(1)-F-C(6)F(5) interaction, which serves as a hook. The reaction proceeds via a sigma bond metathesis where the fluorine ortho to the hook migrates toward H with a relatively low activation energy. All products observed experimentally are accommodated by pathways that involve C-F and C-H bond cleavages.