Wang Xiuxiu, Han Zong-Chang, Wei Wei, Hu Hanshi, Li Pengfei, Sun Peiqing, Liu Xiangzhi, Lv Zhijia, Wang Feng, Cao Yi, Guo Zijian, Li Jun, Zhao Jing
State Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University Nanjing 210023 China
School of Life Sciences, Nanjing University Nanjing 210023 China.
Chem Sci. 2022 May 30;13(24):7269-7275. doi: 10.1039/d1sc07122j. eCollection 2022 Jun 22.
Metal clusters, such as iron-sulfur clusters, play key roles in sustaining life and are intimately involved in the functions of metalloproteins. Herein we report the formation and crystal structure of a planar square tetranuclear silver cluster when silver ions were mixed with human copper chaperone Atox1. Quantum chemical studies reveal that two Ag 5s electrons in the tetranuclear silver cluster fully occupy the one bonding molecular orbital, with the assumption that this Ag cluster is Ag , leading to extensive electron delocalization over the planar square and significant stabilization. This bonding pattern of the tetranuclear silver cluster represents an aromatic all-metal structure that follows a 4 + 2 electron counting rule ( = 0). This is the first time an all-metal aromatic silver cluster was observed in a protein.
金属簇，如铁硫簇，在维持生命过程中发挥着关键作用，并且与金属蛋白的功能密切相关。在此，我们报道了银离子与人铜伴侣蛋白Atox1混合时形成的平面四方四核银簇的结构及晶体结构。量子化学研究表明，四核银簇中的两个Ag 5s电子完全占据一个成键分子轨道，假设该银簇为Ag⁺，从而导致平面四方上的电子广泛离域并显著稳定。这种四核银簇的键合模式代表了一种遵循4n + 2电子计数规则（n = 0）的芳香性全金属结构。这是首次在蛋白质中观察到全金属芳香性银簇。
