A Tetrahedrally Coordinated L₃Fe−N<i>_x</i> Platform that Accommodates Terminal Nitride (Fe^IV⋮N) and Dinitrogen (Fe^I−N₂−Fe^I) Ligands

Abstract

A tetrahedrally coordinated L3Fe-Nx platform that accommodates both terminal nitride (L3FeIVN) and dinitrogen (L3FeI-N2-FeIL3) functionalities is described. The diamagnetic L3FeIVN species featured has been characterized in solution under ambient conditions by multinuclear NMR (1H, 31P, and 15N) and infrared spectroscopy. The electronic structure of the title complex has also been explored using DFT. The terminal nitride complex oxidatively couples to generate the previously reported L3FeI-N2-FeIL3 species. This reaction constitutes a six-electron transformation mediated by two iron centers. Reductive protonation of the nitride complex releases NH3 as a significant reaction product.