Yu Xin, Woods Toby J, Rauchfuss Thomas B
School of Chemical Sciences, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, United States.
J Am Chem Soc. 2025 Jul 30;147(30):26762-26768. doi: 10.1021/jacs.5c07540. Epub 2025 Jul 18.
The preparation, spectroscopy, and structure are described for [Fe(κ-cys)(CN)(CO)] ([]). Otherwise known as complex-B, this coordination complex is an early intermediate in the biosynthesis of the active site of the [FeFe]-hydrogenases. As confirmed by X-ray crystallography, the complex is octahedral with a tridentate cysteinate ligand. The octahedron is completed with two CO ligands and CN, which is trans to thiolate. A second isomer is observed in solution. Complex [] was prepared by treating [Fe(succinimido)(Br)(CN)(CO)] ([]) with cysteinate. From [] the related penicillamine and homocysteine complexes were also prepared. A practical reagent for probing the biosynthetic role of complex-B, called Syn-B-Br, can be produced in good yield from []. Complex [] is prepared by oxidative addition of -bromosuccinimide to [Fe(CN)(CO)]. The work is complemented by CO exchange experiments and DFT calculations.
描述了[Fe(κ-半胱氨酸)(CN)(CO)] ([]）的制备、光谱和结构。这种配位络合物也被称为络合物-B，是[FeFe]-氢化酶活性位点生物合成中的早期中间体。经X射线晶体学证实，该络合物为八面体结构，带有一个三齿半胱氨酸配体。八面体由两个CO配体和与硫醇盐呈反式的CN配体构成。在溶液中观察到了第二种异构体。络合物[]是通过用半胱氨酸处理[Fe(琥珀酰亚胺)(Br)(CN)(CO)] ([]）制备而成的。从[]还制备了相关的青霉胺和高半胱氨酸络合物。一种用于探究络合物-B生物合成作用的实用试剂Syn-B-Br可以从[]以良好的产率制备得到。络合物[]是通过将N-溴代琥珀酰亚胺氧化加成到[Fe(CN)(CO)]上制备而成的。CO交换实验和密度泛函理论计算对这项工作起到了补充作用。
