期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 58, 期 49, 页码 17589-17593出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201908689
关键词
EPR spectroscopy; iron; Mossbauer spectroscopy; nitrides; nitrosyl
资金
- 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
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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