Dinitrogen Activation: A Novel Approach with P/B Intermolecular FLP.

This study explores the reactivity of a new intermolecular P/B frustrated Lewis pair in the context of dinitrogen activation through a push-pull mechanism. The ab initio molecular dynamics model known as atom-centered density matrix propagation plays a pivotal role in elucidating the weakly associated encounter complex. In-depth analysis, mainly through intrinsic reaction coordinate calculations, supports a single-step mechanism. Notably, N₂ activation is observed to proceed through a concerted mechanism, proving slightly endergonic in solvents like toluene and hexane. Furthermore, density functional theory calculations reveal that the N₂ activation reaction becomes kinetically and thermodynamically favorable when it is subjected to a moderately oriented external electric field of 2.57 V nm^-1 along the reaction axis. In addition, natural bonding orbital and extended transition state-natural orbitals for chemical valence analyses contribute to a more profound comprehension of the electron-transfer processes integral to the chemical reaction.