Department of Organic Chemistry, Faculty of Science, Charles University, Hlavova 2030/8, 128 43, Prague 2, Czech Republic.
Departament de Quimica and Institute of Computational Chemistry and Catalysis (IQCC), University of Girona, Campus Montilivi, Girona, 17071, Spain.
Angew Chem Int Ed Engl. 2017 Nov 6;56(45):14057-14060. doi: 10.1002/anie.201707420. Epub 2017 Oct 9.
The generation of iron(V) nitride complexes, which are targets of biomimetic chemistry, is reported. Temperature-dependent ion spectroscopy shows that this reaction is governed by the spin-state population of their iron(III) azide precursors and can be tuned by temperature. The complex [(MePy TACN)Fe(N )] (MePy TACN=N-methyl-N,N-bis(2-picolyl)-1,4,7-triazacyclononane) exists as a mixture of sextet and doublet spin states at 300 K, whereas only the doublet state is populated at 3 K. Photofragmentation of the sextet state complex leads to the reduction of the iron center. The doublet state complex photodissociates to the desired iron(V) nitride complex. To generalize these findings, we show results for complexes with cyclam-based ligands.
铁(V)氮化物配合物的生成，这是仿生化学的目标，据报道。温度依赖的离子光谱表明，该反应受其铁(III)叠氮化物前体的自旋态分布控制，并可通过温度进行调节。配合物[(MePy TACN)Fe(N3)]（MePy TACN=N-甲基-N,N-双(2-吡啶基)-1,4,7-三氮杂环壬烷）在 300 K 时以六重态和双重态的混合物形式存在，而在 3 K 时仅填充双重态。六重态配合物的光解导致铁中心的还原。双重态配合物光解生成所需的铁(V)氮化物配合物。为了推广这些发现，我们展示了基于环戊烷的配体的配合物的结果。
