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- Title
Decay of Iron(V) Nitride Complexes By a NN Bond-Coupling Reaction in Solution: A Combined Spectroscopic and Theoretical Analysis.
- Authors
Krahe, Oliver; Bill, Eckhard; Neese, Frank
- 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 FeVN→FeII-NN-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.
- Subjects
IRON compounds; NITROGEN; COUPLING reactions (Chemistry); CRYOGENICS; MOSSBAUER spectroscopy; MASS spectrometry; HABER-Bosch process
- Publication
Angewandte Chemie International Edition, 2014, Vol 53, Issue 33, p8727
- ISSN
1433-7851
- Publication type
Article
- DOI
10.1002/anie.201403402