The extreme π-loading of a (CCC-NHC) pincer Ta(V) bis(imido) complex was previously reported. This complex catalyzes the cyclization of α,ω-aminoalkenes (2,2-diphenylpent-4-en-1-amine) to produce three different products in varying proportions: cyclic imine from oxidative amination (OA), reduction product (RP) from hydrogenated substrate, and hydroamination (HA) et al. Organometallics 2016, 35, 3452). Various plausible pathways for the reactions generating cyclic imine product from oxidative amination, the reduction of substrate from hydrogen transfer, the cyclic amine product from hydroamination, and the dehydrogenation of hydroamination product were evaluated using density functional theory computations. RP is the thermodynamic product, while OA and HA are the kinetic products, with HA being lower in energy than OA. Multiple pathways for the generation of OA product were examined. The lowest free energy of activation (ΔG ⧧ ) of the rate-determining-step (RDS) during the oxidative amination was calculated to be 28.8 kcal mol −1 . The ΔG ⧧ of the RDS for the generation of reduction product is 42.8 kcal mol −1 and for the generation of hydroamination product is 41.8 kcal mol −1 . The overall turnover-limiting step of the proposed catalytic cycle of the conversions of substrate 3 is the regeneration of the Ta(V) bis(imido) intermediate 7 from Ta(V)-hydride amido intermediate 13 (42.8 kcal mol −1 , TS-19-7). An amido hydride Ta intermediate 13 is the computed resting state of the proposed catalytic cycle. High temperature significantly favored the formation of OA-4 and RP-5 and also promoted the dehydrogenation of HA-6. An alternative for the generation of OA-4 with the participation of the NHC as a proton shuttle and through a σ N -π-σ C isomerization pathway is also discussed. The computational results are consistent with the experimentally observed product ratios and selectivity.