Importance of Nitrogen–Hydrogen Bond pKa in the Catalytic Coupling of Alkenes and Amines by Amidate Tantalum Complexes: A Computational Study

Density functional theory (DFT) was carried out to study the impact of substituents with different electronic properties upon hydrogen transfer as the rate-determining step in the hydroaminoalkylation catalytic cycle in order to determine the character of the hydrogen atom in the transition state. In the transition state of the rate-determining step, an N-methylaniline substrate ligates to Ta and transfers its hydrogen to the α-carbon of a five-membered tantallacycle and a Ta–C bond is thus broken. Study of the activation energy barriers resulting from the different para- and meta-substituted N-methylanilines and their correlation with computed pKa and bond dissociation free energy (BDFE) values of the N-methylanilines show more obvious correlations between pKa and ΔG‡ values. Assessing the asynchronicity parameter (η) for the studied substituents reveals that pKa is a larger driving force in the rate-determining hydrogen transfer reaction than the BDFE, which suggest a reasonable amount of protic character in the transition state, and possible routes to the design of more active catalysts with greater substrate scope.