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

Area of Science:

• Organometallic Chemistry
• Computational Chemistry

Background:

• Frustrated Lewis pairs (FLPs) are key to small molecule activation.
• Dinitrogen (N2) activation remains a significant challenge in chemistry.

Purpose of the Study:

• To investigate the reactivity of a novel intermolecular P/B FLP for N2 activation.
• To elucidate the mechanism of N2 activation via a push-pull mechanism.

Main Methods:

• Ab initio molecular dynamics (AIMD) using atom-centered density matrix propagation.
• Intrinsic reaction coordinate (IRC) calculations.
• Density functional theory (DFT) and natural bonding orbital (NBO) analyses.

Main Results:

• A single-step, concerted mechanism for N2 activation was identified.
• The reaction was slightly endergonic in nonpolar solvents.
• An external electric field (2.57 V nm-1) significantly enhanced kinetic and thermodynamic favorability.
• Electron transfer processes were analyzed using NBO and ETS-NOCV.

Conclusions:

• The P/B FLP facilitates N2 activation through a concerted mechanism.
• External electric fields can be a powerful tool to control and promote FLP-mediated reactions.
• This work provides a deeper understanding of N2 activation mechanisms and electron dynamics.