Liu Wen-Yan, Li Ying-Zhou, Yu Jiu-Hong, Yuan Zhi-Rui, Yang Peng-Fei, Azam Mohammad, Sun Di
School of Chemistry and Chemical Engineering, Qilu University of Technology (Shandong Academy of Sciences), Ji'nan, 250353, P. R. China.
School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials, Shandong University, Ji'nan, 250100, P. R. China.
Chem Asian J. 2025 Aug;20(16):e00438. doi: 10.1002/asia.202500438. Epub 2025 May 29.
As the new type of molecular catalysts, hemilabile ligand-protected Au nanoclusters hold greater promise in realizing a better trade-off between catalytic activity and structural stability. Despite the large amount of Au nanoclusters (co-)protected by organic nitrogen ligands, little has been known about those containing dynamically labile Au─N bonds, where the hemilabile ligands are solely limited to pyridyl-phosphine. In this study, we chose imidazolyl-phosphine (dpim) as the main protecting ligand and synthesized a new tetracationic cluster [Au(dpim)(dppe)Cl] (Au-S, dppe = PhP(CH)PPh), which was structurally characterized crystallographically, spectroscopically, and computationally. Albeit the similar electronic structure of the Au core, Au-S possesses different ligand arrangements and positive charges from those of its two reported structural analogues, and thus they may serve as an ideal cluster triad for comparatively studying the ligand/charge effect on their catalytic activities. This work proved the potential of imidazolyl phosphine as a versatile hemilabile ligand in the syntheses of Au NCs with labile Au─N bonds. The imidazolyl-phosphines are more amenable to derivatizations, which provides a new opportunity for further enriching the library of hemilabile ligand-protected Au NCs with potentially better catalytic performance.
作为新型分子催化剂，半不稳定配体保护的金纳米团簇在实现催化活性与结构稳定性之间更好的平衡方面具有更大的潜力。尽管有大量由有机氮配体（共）保护的金纳米团簇，但对于那些含有动态不稳定金-氮键的团簇却知之甚少，其中半不稳定配体仅局限于吡啶基膦。在本研究中，我们选择咪唑基膦（dpim）作为主要保护配体，合成了一种新的四核簇[Au(dpim)(dppe)Cl]（Au-S，dppe = PhP(CH)PPh），并通过晶体学、光谱学和计算对其结构进行了表征。尽管金核的电子结构相似，但Au-S与其两个已报道的结构类似物具有不同的配体排列和正电荷，因此它们可作为理想的簇三联体，用于比较研究配体/电荷对其催化活性的影响。这项工作证明了咪唑基膦作为一种通用的半不稳定配体在合成具有不稳定金-氮键的金纳米团簇中的潜力。咪唑基膦更易于衍生化，这为进一步丰富具有潜在更好催化性能的半不稳定配体保护的金纳米团簇库提供了新的机会。
