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The transfer of protons and electrons to metal-ligand multiply-bonded species is a key step in the mechanism of many bond activation processes. In this regard, terminally-bonded phosphinimides (PN) are isolobal analogues of oxos and imidos and should enable late transition metal complexes featuring terminal PNs to engage in H + /e −  transfer processes. Recently, we developed a rigid, multidentate PN framework intended to stabilize terminally bonded PN ligands at late, first row transition metals. Herein, we report the synthesis, structure, and spectroscopic characterization of mononuclear Fe III  complexes featuring exclusively terminal PN coordination. Magnetic susceptibility and EPR spectroscopic data are consistent with  S  = 5/2 spin ground states. Proton transfer reactivity both via 1,2-addition across a PN − Fe III  moiety and 1,2-elimination from a ferric phosphinimine (PNH) moiety is observed. Hydrogen atom transfer reactivity is observed upon oxidation of the PN − Fe III  complex, resulting in formation of a PNH − Fe III  species. A combination of electrochemical,  pKa  measurement, and DFT studies support an N − H bond dissociation free energy of ∼90 kcal/mol for a PNH − Fe III  species, and serve to highlight a reactive, transient PN − Fe IV  species. Combined, our results highlight terminal, late transition metal-PN moieties as redox-active superbases competent for efficient hydrogen atom abstraction processes.

N − H bond dissociation free energy of a terminal iron phosphinimine