配体引导铜基配合物的合成、表征及催化性能

摘要/Abstract

摘要： 以酰胺类化合物和偶氮化合物为配体制备了五种不同的含Cu/Zn配合物。通过单晶XRD、核磁氢谱等表征确定了配合物的具体结构,结果发现改变合成条件使配合物的构型以及中心金属的价态发生变化。此外,电喷雾质谱测试也证实了不同化合物中金属铜的不同价态。为了探究不同结构对配合物性质的影响,选取硫醚氧化成砜的催化反应作为研究对象,探索出了最优的催化反应条件,同时发现中心金属为Zn的配合物催化效果最佳,在60 ℃条件下反应1.75 h苯甲基硫醚可完全转化为砜,Cu²⁺配合物的催化效率高于Cu⁺的配合物。由此,提出了一个可能的催化反应机理,即氧化剂先与中心金属结合形成过氧配合物,然后再氧化底物形成对应的亚砜或砜。

关键词: 吡啶酰胺配体, 偶氮配体, 铜基配合物, 气相扩散结晶, 电喷雾质谱, 硫醚氧化催化

Abstract: Five different Cu/Zn contained complexes were prepared using amide and azoic compound as ligand. The structures of these complexes were determined by single-crystal XRD and NMR spectra. The results show that the coordination mode and valence state of the central metal would change if the synthesis conditions were changed. In addition, electrospray mass spectrometry also confirms the different valence states of copper in different compounds. In order to explore the effects of different structures on the properties of complexes, the thioether oxidation catalysis reaction was selected as the research object. The optimal catalytic reaction conditions were explored, and it was found that the Zn based complex has the best catalytic effect. The phenylmethyl sulfide could be completely converted into sulfone at 60 ℃ for 1.75 h. Also, the catalytic efficiency of Cu²⁺ complexes is higher than that of Cu⁺ complexes. Thus, a possible catalytic reaction mechanism is proposed, in which the oxidant first binds to the central metal to form a peroxide, and then oxidizes the substrate to form corresponding sulfoxide or sulfone.

Key words: pyridinamide ligand, azo ligand, copper based complex, vapor phase diffusion crystallization, electrospray mass spectrometry, sulfide oxidation catalysis

中图分类号:

O611

张银, 于卫东. 配体引导铜基配合物的合成、表征及催化性能[J]. 人工晶体学报, 2023, 52(6): 1145-1153.

ZHANG Yin, YU Weidong. Synthesis, Characterization and Catalytic Properties of Copper Based Complexes Guided by Ligands[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2023, 52(6): 1145-1153.

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