Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 58, Issue 49, Pages 17589-17593Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201908689
Keywords
EPR spectroscopy; iron; Mossbauer spectroscopy; nitrides; nitrosyl
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Funding
- Max-Planck Society
- Ministry of Science and Technology of Taiwan [MOST 105-2113-M-003-005-MY3]
- MOST-DAAD Project-Based Personnel Exchange Program [MOST 107-2911-I-003-502, DAAD 57320810]
- MPI-CEC
- MPI-KOFO
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Terminal metal nitrides have been proposed as key intermediates in a series of pivotal chemical transformations. However, exploring the chemical activity of transient tetragonal iron(V) nitrides is largely impeded by their facile dimerization in fluid solutions. Herein, in situ EPR and Mossbauer investigations are presented of unprecedented oxygenation of a paramagnetic iron(V) nitrido intermediate, [(FeN)-N-V(cyclam-ac)](+) (2, cyclam-ac(-)=1,4,8,11-tetraazacyclotetradecane-1-acetate anion), yielding an iron nitrosyl complex, [Fe(NO)(cyclam-ac)](+) (3). Further theoretical studies suggest that during the reaction a closed-shell singlet O atom is transferred to 2. Consequently, the N-O bond formation does not follow a radical coupling mechanism proposed for the N-N bond formation but is accomplished by three mutual electron-transfer pathways between 2 and the O atom donor, thanks to the ambiphilic nature of 2.
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