The monomeric metallocenecerium hydride, CP'(CeH (Cp' = 1,2,4-tri-tert-butylcyclopentadienyl), reacts instantaneously with CH)(F, but slower with CH)(F)(, to give CP')(CeF and CH)(2)(3)(2)(2)(2)(4) (in each case, a net H for F exchange reaction. The hydride reacts very slowly with CHF)(, and not at all with CF)(, to give CP'2CeF, H)(, and 1,2,4- and 1,3,5-tri-tert-butylbenzene. The substituted benzenes are postulated to result from trapping of a fluorocarbene fragment derived by a-fluoride abstraction from Cp')(CeCF)(. The fluoroalkyl, Cp')(CeCF)(, is generated by reaction of CP')(CeH and Me)(SiCF)(3)(4)(2)(2)(3)(2)(3)(2)(3)(3) (or by reaction of the metallacycle, [(Cp')(Me)(C))(C)(H)(C(Me)()CH)(]Ce, with CHF)(, and its existence is inferred from the products of decomposition, which are Cp)(CeF, the isomeric tri-tert-butylbenzenes and in the case of Me)(SiCF)(, Me)(SiH. The fluoroalkyls, CP')(CeCH)(F and CP')(CeCHF)(, generated from the metallacycle and CH)(F and CH)(F)(, respectively, are also inferred by their decomposition products, which are CP')(CeF, CH)(, and CHF, respectively, which are trapped. DFT(B3PW91) calculations have been carried out to examine several reaction paths that involve CH and CF bond activation. The calculations show that the CH activation by CP)(CeH proceeds with a low barrier. The carbene ejection and trapping by H)(3)(2)(5)(2)(2)(2)(3)(2)(3)(3)(3)(2)(2)(2)(2)(3)(2)(2)(2)(2)(2)(2) (is the rate-determining step, and the barrier parallels that found for reaction of H)(2) (with CH)(, CHF, and CF)(2)(2). The barrier of the rate-determining step is raised as the number of fluorines increases, while that of the CH activation path is lowered as the number of fluorines increases, which parallels the acidity.