Theoretical mechanistic insights into dinitrogen cleavage by a dititanium hydride complex bearing PNP-pincer ligands

The mechanism of dinitrogen cleavage by a PNP-coordinated dititanium polyhydride complex has been computationally investigated. A multi-state reactivity scenario has been disclosed for the whole process of N-2 coordination and activation. Remarkably, the H-2 elimination prior to the N-N cleavage is accomplished by the coupling of two terminal hydrides, and planar PNP-pincer ligand could stabilize the corresponding transition state. Besides, the tetrahydrofuran (THF) solvent could also promote the H-2 elimination due to the similar polarity of the corresponding intermediates or transition states to THF molecule.

Automated summary

The mechanism of dinitrogen cleavage by a PNP-coordinated dititanium polyhydride complex has been computationally investigated, revealing a multi-state reactivity scenario for the process. Prior to N-N cleavage, H-2 elimination is facilitated by coupling two terminal hydrides, with stabilization provided by a planar PNP-pincer ligand. Additionally, the THF solvent promotes H-2 elimination due to the similar polarity of intermediates or transition states.