文献类型：期刊文献

英文题名：Iron(II/III) α-hydroxycarboxylates toward the local coordination environments of FeFe-cofactor in Fe-nitrogenase

作者：Zhu, Xing-Yi[1];Xie, Zhen-Lang[2];Wang, Si-Yuan[3];Jin, Wan-Ting[4];Zhou, Zhao-Hui[1]

机构：[1]Xiamen Univ, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China;[2]Guangdong Ocean Univ, Coll Food Sci & Engn, Yangjiang 529500, Peoples R China;[3]Heilongjiang Univ Chinese Med, Sch Pharm, Haerbin 150040, Peoples R China;[4]Quzhou Univ, Coll Chem & Mat Engn, Quzhou 324000, Peoples R China

年份：2026

卷号：278

外文期刊名：JOURNAL OF INORGANIC BIOCHEMISTRY

收录：SCI-EXPANDED(收录号：WOS:001675356300001)、、WOS

基金：We thank the support from the National Natural Science Foundation of China (22179110) and the Guangdong Basic and Applied Basic Research Foundation (2024A1515110030) .

语种：英文

外文关键词：Iron alpha-hydroxycarboxylate; Fe-only nitrogenase; Active site; Local chelated environment

外文摘要：Enantiomerically pure iron(II/III) lactates Lambda-FeII(S-Hlact)2(H2O)2 (1), Na[Lambda-FeIII(S-Hlact)2(S-lact)]& sdot;3.5H2O (2a) and Na[Delta-FeIII(R-Hlact)2(R-lact)]& sdot;3.5H2O (2b), along with iron(II/III) citrates (H2pz)2[FeIII 2 (cit)2(H2O)2]& sdot;2H2O (3) and [FeII(Hpz)4]n[FeIII 2 (cit)2(Hpz)2]n & sdot;2n(Hpz)& sdot;0.25nH2O (4) (H2lact = lactic acid, H4cit = citric acid, Hpz = pyrazole) have been obtained. In 1 and 2, lactates chelate with iron bidentately through alpha-hydroxy/alpha-alkoxy and alpha-carboxy groups, respectively, forming stable five-membered chelated rings. Strong intermolecular hydrogen bonds have been found between alpha-hydroxy and alpha-alkoxy groups, with strong electron delocalization. For 3, citrate chelates one of the iron centers in a tridentate mode via its alpha-alkoxy, alpha-carboxy, and beta-carboxy groups, leaving protonated pyrazole free. Further substitution of the coordinated water molecule in 3 results in the formation of mixed-valent pyrazole iron(II/III) citrate 4. The iron lactates and citrates show resemblance to the local environment of the active site of homocitrate and imidazole-coordinated FeFe-cofactor in Fe-only nitrogenase. The biological relevance has been discussed in details.