Shi Quanquan, Qin Zhaoxian, Ping Guichen, Liu Shuang, Xu Hui, Li Gao
College of Science & Inner Mongolia Key Laboratory of Soil Quality and Nutrient Resource, Inner Mongolia Agricultural University Hohhot 010018 China.
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences Dalian 116023 China
RSC Adv. 2020 Jun 5;10(36):21650-21655. doi: 10.1039/d0ra02178d. eCollection 2020 Jun 2.
The coordination motif of alkynly with a metal atom is versatile and plays a pivotal role in tailoring the kernel configuration of the atomically precise metal nanoclusters. In this study, we synthesized a new mono-valent Au(I)Ag(I)(CHNO)(PhP) alloy cluster with a very high yield of >90%, which is well characterized by a serial of technologies, UV-vis, X-ray single crystal diffraction (SCXRD) and FT-IR. The SCXRD analysis shows the alloy cluster is composed of a quadrangular AuAg kernel protected by four alkynyl and two phosphine ligands. Intriguingly, a new divergent alkyne-metal coordination model is revealed in this cluster, the alkynyl ligands selectively bind to Au and Ag atoms σ- and π-bond configurations and adopt a VI-shaped alkynyl-M motif. It is distinct from the convergent motif observed in big clusters featuring an IV- or V-shaped alkynyl-M motif due to the steric effect. Finally, the titanium oxide-supported AuAg cluster catalysts show good catalytic performance in the multicomponent coupling reaction of alkynes, aldehydes and amines.
炔基与金属原子的配位模式具有多样性,在定制原子精确的金属纳米团簇的核心结构中起着关键作用。在本研究中,我们以超过90%的高产率合成了一种新型单价Au(I)Ag(I)(CHNO)(PhP)合金团簇,该团簇通过一系列技术进行了充分表征,包括紫外可见光谱、X射线单晶衍射(SCXRD)和傅里叶变换红外光谱(FT-IR)。SCXRD分析表明,该合金团簇由一个四边形AuAg核心组成,被四个炔基和两个膦配体保护。有趣的是,在该团簇中揭示了一种新的发散型炔基金属配位模型,炔基配体以σ键和π键构型选择性地与Au和Ag原子结合,并采用VI形炔基-M基序。由于空间效应,它与在具有IV形或V形炔基-M基序的大团簇中观察到的收敛型基序不同。最后,氧化钛负载的AuAg团簇催化剂在炔烃、醛和胺的多组分偶联反应中表现出良好的催化性能。