Jiangsu Collaborative Innovation Centre of Biomedical Functional Materials and Jiangsu Key Laboratory of New Power Batteries, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing, Jiangsu, 210023, China.
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, 02138, USA.
Angew Chem Int Ed Engl. 2019 Nov 11;58(46):16469-16473. doi: 10.1002/anie.201908968. Epub 2019 Sep 26.
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*) W Fe (μ -N) S L ] (Tp*=tris(3,5-dimethyl-1-pyrazolyl)hydroborate(1-), L=Cl or Br ). Fe Mössbauer study discloses metal oxidation states of W Fe Fe 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.
自从在钼依赖型氮酶的 FeMo 辅因子中发现间隙碳化物以来，人们一直在研究将单价 2p 配体掺入到铁-硫簇的核心中，但事实证明这是一个合成挑战。在此，合理化了两种不同的合成途径，以将氮化物配体安装到 W-Fe-S 簇的靶向位置，从而生成前所未有的氮化物配位的铁-硫簇，即(Tp*)WFe(μ-N)SL,L=Cl 或 Br)。Fe Mössbauer 研究揭示了 WFeFe 的金属氧化态具有局域电子分布，类似于静止状态下 FeMo 辅因子的中价铁中心。Mössbauer 数据与 Fe-S 簇的经验线性关系吻合较好，表明氮化物和硫化物在这种簇中的配体行为相似，为氮酶样环境中的还原氮提供了有用的参考。
