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Controlled Incorporation of Nitrides into W‐Fe‐S Clusters
Author(s) -
Xu Gan,
Zhou Jie,
Wang Zheng,
Holm Richard H.,
Chen XuDong
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201908968
Subject(s) - nitrogenase , nitride , chemistry , sulfur , carbide , sulfide , crystallography , monatomic ion , ligand (biochemistry) , mössbauer spectroscopy , metal , oxidation state , inorganic chemistry , cofactor , nitrogen , nitrogen fixation , organic chemistry , enzyme , biochemistry , receptor , layer (electronics)
Incorporation of monatomic 2p ligands into the core of iron–sulfur clusters has been researched since the discovery of interstitial carbide in the FeMo cofactor of Mo‐dependent nitrogenase, but has proven to be a synthetic challenge. Herein, two distinct synthetic pathways are rationalized to install nitride ligands into targeted positions of W‐Fe‐S clusters, generating unprecedented nitride‐ligated iron–sulfur clusters, namely [(Tp*) 2 W 2 Fe 6 (μ 4 ‐N) 2 S 6 L 4 ] 2− (Tp*=tris(3,5‐dimethyl‐1‐pyrazolyl)hydroborate(1−), L=Cl − or Br − ). 57 Fe Mössbauer study discloses metal oxidation states of W IV 2 Fe II 4 Fe III 2 with localized electron distribution, which is analogous to the mid‐valent iron centres of FeMo cofactor at resting state. Good agreement of Mössbauer data with the empirical linear relationship for Fe–S clusters indicates similar ligand behaviour of nitride and sulfide in such clusters, providing useful reference for reduced nitrogen in a nitrogenase‐like environment.