Jiangsu Collaborative Innovation Center of Biomedical Functional Materials and Jiangsu Key Laboratory of New Power Batteries, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, Jiangsu, China.
State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, Jiangsu, China.
Inorg Chem. 2022 Mar 7;61(9):4150-4158. doi: 10.1021/acs.inorgchem.1c03998. Epub 2022 Feb 24.
The rational synthesis of iron-sulfur clusters with excellent control of the core ligands has been a significant challenge in biomimetic chemistry. In this work, the rational construction of versatile Mo-Fe-S cubane clusters was realized using a LEGO strategy. (LEGO is a line of plastic construction toys consisting of various interlocking plastic bricks which can be assembled and connected in different ways to construct versatile objects. Herein we use "LEGO strategy" as an analogy for the stepwise synthetic methodology, and we use "brick" to represent a corner atom of the cubane structure.) Through careful synthetic control, the ⟨Fe⟩, ⟨S⟩, and ⟨Cl⟩ bricks were mounted piece-by-piece onto the basic ⟨MoS⟩ frame to stepwise construct the incomplete cubane core ⟨MoFeSCl⟩ and the complete cubane core ⟨MoFeSCl⟩. The significantly elongated Fe-Cl bonds for the bridging chlorides in the ⟨MoFeSCl⟩ and ⟨MoFeSCl⟩ cores permit ligand metatheses to introduce 2 donors at the bridging sites, which used to be a challenge in traditional iron-sulfur chemistry. Therefore, in subsequent controlled reactions, the bridging ⟨Cl⟩ bricks of the ⟨MoFeSCl⟩ and ⟨MoFeSCl⟩ frames could be easily replaced by ⟨N⟩ , ⟨O⟩, or ⟨S⟩ bricks to generate the ⟨MoFeSN⟩, ⟨MoFeSO⟩, ⟨MoFeSN⟩, and ⟨MoFeS⟩ cluster cores, demonstrating more choices for the LEGO synthetic strategy. The series of Mo-Fe-S clusters and their derivatives, together with related synthetic strategies, offers a good platform and methodology for biomimetic chemistry in relation to nitrogenase, especially the FeMo cofactor.
具有优异核配体控制能力的铁硫簇的合理合成一直是仿生化学中的一个重大挑战。在这项工作中，使用乐高策略实现了多功能 Mo-Fe-S 立方烷簇的合理构建。（乐高是一系列由各种互锁塑料积木组成的塑料建筑玩具，可以以不同的方式组装和连接，以构建各种物体。在这里，我们将“乐高策略”类比为逐步合成方法，并用“积木”代表立方烷结构的角原子。）通过仔细的合成控制，将 ⟨Fe⟩、 ⟨S⟩和 ⟨Cl⟩ 积木逐一安装到基本的 ⟨MoS⟩ 框架上，逐步构建不完整的立方烷核 ⟨MoFeSCl⟩ 和完整的立方烷核 ⟨MoFeSCl⟩。桥接氯在 ⟨MoFeSCl⟩ 和 ⟨MoFeSCl⟩ 核中的显著拉长的 Fe-Cl 键允许配体交换在桥接位置引入 2 个供体，这在传统的铁硫化学中一直是一个挑战。因此，在随后的受控反应中， ⟨MoFeSCl⟩ 和 ⟨MoFeSCl⟩ 框架的桥接 ⟨Cl⟩ 积木可以很容易地被 ⟨N⟩、 ⟨O⟩或 ⟨S⟩ 积木取代，生成 ⟨MoFeSN⟩、 ⟨MoFeSO⟩、 ⟨MoFeSN⟩ 和 ⟨MoFeS⟩ 簇核，为乐高合成策略提供了更多选择。这一系列的 Mo-Fe-S 簇及其衍生物，以及相关的合成策略，为与氮酶相关的仿生化学，特别是 FeMo 辅因子，提供了一个很好的平台和方法。
