The reaction between monomeric bis(1,2,4-tri-tert-butylcyclopentadienyl)cerium hydride, CP'2CeH, and several hydrofluorobenzene derivatives is described. The aryl derivatives that are the primary products, CP'Ce-2(C6H5-xFx) where x = 1,2,3,4, are thermally stable enough to be isolated in only two cases, since all of them decompose at different rates to CP'2CeF and a fluorobenzyne; the latter is trapped by either solvent when C6D6 is used or by a Cp'H ring when C6D12 is the solvent. The trapped products are identified by GC/MS analysis after hydrolysis. The aryl derivatives are generated cleanly by reaction of the metallacycle, Cp'((Me3C)(2)C5H2C(Me-2)CH2)Ce, with a hydrofluorobenzene, and the resulting arylcerium products, in each case, are identified by their H-1 and F-19 NMR spectra at 20 degrees C. The stereochemical principle that evolves from these studies is that the thermodynamic isomer is the one in which the CeC bond is flanked by two ortho-CF bonds. This orientation is suggested to arise from the negative charge that is localized on the ipso-carbon atom due to C-o(delta+)F-o(delta-) polarization. The preferred regioisomer is determined by thermodynamic rather than kinetic effects; this is illustrated by the quantitative, irreversible solid-state conversion at 25 degrees C over two months of CP'Ce-2(2,3,4,5-C6HF4) to CP'Ce-2(2,3,4,6-C6HF4), an isomerization that involves a CeC(ipso) for C(ortho)F site exchange.