Dinitrogen chemistry from trigonally coordinated iron and cobalt platforms.

This report establishes that trigonally coordinated "[PhBPiPr3]M" platforms (M = Fe, Co) will support both pi-acidic (N2) and pi-basic (NR) ligands at a fourth binding site. The N2 complexes of iron that are described are the first thoroughly characterized examples to exhibit a 4-coordinate geometry. Methylation of monomeric {Fe0(N2)-} and {Co0(N2)-} species successfully derivatizes the beta-N atom of the coordinated N2 ligand and affords the diazenido products {FeII(N2Me)} and {CoII(N2Me)}, respectively. One-electron oxidation of the mononuclear M0(N2)- species produces dinuclear and synthetically versatile MI(N2)MI complexes. These latter species provide clean access to the chemistry of the "[PhBPiPr3]MI" subunit. For example, addition of RN3 to MI(N2)MI results in oxidative nitrene transfer to generate [PhBPiPr3]MNR with concomitant N2 release.