Isotopically labeled alkyl zirconocene complexes of the form (CpRn)(2)Zr(CH2CDR'(2))(X) (CpRn = alkyl-substituted cyclopentadienyl; R' = H, alkyl group; X = H, D, Me) undergo isomerization of the alkyl ligand as well as exchange with free olefin in solution under ambient conditions, Increasing the substitution on the Cp ring results in slower isomerization reactions, but these steric effects are small. In contrast, changing X has a very large effect on the rate of isomerization. Pure sigma-bending ligands such as methyl and hydride promote rapid isomerization, whereas pi-donor ligands inhibit beta-H elimination and hence alkyl isomerization. For (eta(5)-C5H5)(2)Zr(R)(Cl), internal alkyl complexes have been observed for the first time. The rate of isomerization depends on the length of the alkyl group: longer alkyl chains (heptyl, hexyl) isomerize faster than shorter chains (butyl). The transient intermediate species have been identified by a combination of isotopic labeling and H-1, H-2, and C-13 NMR experiments. The solid-state structure of the zirconocene cyclopentyl chloride complex, Cp2Zr(cyclo-C5H9)(Cl), has been determined by X-ray diffraction.