Description:
<jats:title>Abstract</jats:title><jats:p>Cryogenically trapped Fe<jats:sup>V</jats:sup> nitride complexes with cyclam‐based ligands were found to decay by bimolecular reactions, forming exclusively Fe<jats:sup>II</jats:sup> compounds. Characterization of educts and products by Mössbauer spectroscopy, mass spectrometry, and spectroscopy‐oriented DFT calculations showed that the reaction mechanism is reductive nitride coupling and release of dinitrogen (2 Fe<jats:sup>V</jats:sup>N→Fe<jats:sup>II</jats:sup>‐NN‐Fe<jats:sup>II</jats:sup>→2 Fe<jats:sup>II</jats:sup>+N<jats:sub>2</jats:sub>). The reaction pathways, representing an “inverse” of the Haber–Bosch reaction, were computationally explored in detail, also to judge the feasibility of yielding catalytically competent Fe<jats:sup>V</jats:sup>(N). Implications for the photolytic cleavage of Fe<jats:sup>III</jats:sup> azides used to generate high‐valent Fe nitrides are discussed.</jats:p>