陈旭东教授课题组在ANGEWANDTE CHEMIE-INTERNATIONAL EDITION发表研究论文
Controlled Incorporation of Nitrides into W-Fe-S Clusters
Xu, G (Xu, Gan)[ 1,2 ] ; Zhou, J (Zhou, Jie)[ 1,2 ] ; Wang, Z (Wang, Zheng)[ 1,2 ] ; Holm, RH (Holm, Richard H.)[ 3 ] ; Chen, XD (Chen, Xu-Dong)[ 1,2 ]*（陈旭东）
[ 1 ] Nanjing Normal Univ, Sch Chem & Mat Sci, Jiangsu Collaborat Innovat Ctr Biomed Funct Mat, Nanjing 210023, Jiangsu, Peoples R China
[ 2 ] Nanjing Normal Univ, Sch Chem & Mat Sci, Jiangsu Key Lab New Power Batteries, Nanjing 210023, Jiangsu, Peoples R China
[ 3 ] Harvard Univ, Dept Chem & Chem Biol, Cambridge, MA 02138 USA
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION，201909, DOI: 10.1002/anie.201908968
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)W2Fe6(mu(4)-N)(2)S6L4](2-) (Tp*=tris(3,5-dimethyl-1-pyrazolyl)hydroborate(1-), L=Cl- or Br-). Fe-57 Mossbauer study discloses metal oxidation states of (W2Fe4Fe2III)-Fe-IV-Fe-II with localized electron distribution, which is analogous to the mid-valent iron centres of FeMo cofactor at resting state. Good agreement of Mossbauer 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.