Investigations of the syntheses, structural characterization, and relative stabilities of the cyclopentadienyl, amidinate Zr cycloalkylmethyl complexes, (CPAM)Zr(X)[CH2(cyclo-CmH2m-1)] (CPAM = (η5-C5Me5)[(N,N′)-κ2-N(Et)-C(Me)N(t-Bu)]) for X = Cl and m = 3 (1a), 4 (1b) and 5 (1c) and for X = Me, and m = 4 (2b), and of the corresponding isomeric ω-alkenyl complexes, (CPAM)Zr(Cl)[CH2(CH2)nCH2CH = CH2] for n = 0 (3a), 1 (3b) and 2 (3c), have been conducted. Hydrozirconation of methylenecyclopropane by (CPAM)Zr(X)Cl (X = H or D) (8), which is generated in situ through hydrogenolysis of the Zr-Si bond of (CPAM)Zr(SiMe2Ph)Cl (7), provided a high yield of 3a due to rapid isomerization of transiently generated 1a. In contrast, crystalline 1b could be isolated in high yield via hydrozirconation of methylenecyclobutane by 8, and it has been structurally characterized by X-ray crystallography. Thermolysis of 1b in solution provided a quantitative yield of 3b, while quantitative production of 1c was achieved through intramolecular cyclization of 3c by reversible chloride abstraction that was catalyzed by addition of the ion pair, {(CPAM)Zr(Me)}{B(C6F5)4} 10. The cyclobutylmethyl complex 2b was also prepared from 1b through traditional methylation using MeLi, and it too was structurally characterized by X-ray crystallography. In solution, 2b thermally decomposes at 25 °C to an intractable mixture. Finally, reaction of 2b with a stoichiometric amount of the borate B1 provided the corresponding ion pair complex, {(CPAM)Zr[CH2CH2CH2CH = CH2]}{B(C6F5)4} (9) in which the terminal alkenyl group is intramolecularly coordinated to the transition metal center as determined by 1H NMR spectroscopy. The results of a DFT (B3LYP / LANL2DZ (Zr) / 6-31G**) computational investigation for the 1b to 3b isomerization and for the structure of 9 are also included.