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

Abstract

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 N₂ coordination and activation. Remarkably, the H₂ 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 H₂ elimination due to the similar polarity of the corresponding intermediates or transition states to THF molecule.