Decay of Iron(V) Nitride Complexes By a NN Bond‐Coupling Reaction in Solution: A Combined Spectroscopic and Theoretical Analysis |
| |
Authors: | Oliver Krahe Dr Eckhard Bill Prof?Dr Frank Neese |
| |
Institution: | Max‐Planck Institute for Chemical Energy Conversion, Stiftstrasse 34–36, 45470 Mülheim an der Ruhr (Germany) http://www.cec.mpg.de |
| |
Abstract: | Cryogenically trapped FeV nitride complexes with cyclam‐based ligands were found to decay by bimolecular reactions, forming exclusively FeII 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 FeV?N→FeII‐N?N‐FeII→2 FeII+N2). 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 FeV(N). Implications for the photolytic cleavage of FeIII azides used to generate high‐valent Fe nitrides are discussed. |
| |
Keywords: | FeV nitrides iron mass spectrometry Mö ssbauer spectroscopy nitride coupling |
|
|