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含酰腙配体的半三明治型钌配合物:酰肼α-烷基化反应中的合成及催化活性

Half-sandwich ruthenium complexes with acylhydrazone ligands: synthesis and catalytic activity in the -alkylation of hydrazides.

作者信息

Li Heng, Wang Ke, Yang Lin, Luo Yu-Zhou, Yao Zi-Jian

机构信息

School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai, 201418, China.

Scientific Research Office, Guangzhou College of Commerce, Guangzhou, 511363, China.

出版信息

Dalton Trans. 2024 Feb 6;53(6):2797-2806. doi: 10.1039/d3dt04078j.

DOI:10.1039/d3dt04078j
PMID:38226891
Abstract

Novel half-sandwich ruthenium complexes termed [(-cymene)RuClL] were synthesized by chelating arylhydrazone ligands with [(-cymene)RuCl] and were then fully characterized using different spectroscopic and analytical techniques. The crystal structure of complex 4 indicated that the hydrazone ligands bonded to the ruthenium ion in a bidentate manner through the imine nitrogen and imidazolate oxygen, exhibiting a pseudo-octahedral geometry centered by the ruthenium atom. The as-fabricated air and moisture stable half-sandwich ruthenium complexes demonstrated excellent catalytic activity towards the -alkylation of hydrazides under mild conditions. Under the catalysis of ruthenium complexes, acyl hydrazides were reacted with different types of alcohols in a one-pot reaction, resulting in -alkylation hydrazides with different substituents. This catalyst exhibited characteristics such as high catalytic efficiency, broad substrate scope, and mild reaction conditions, indicating that it has great potential for industrial applications.

摘要

通过将芳基腙配体与[(对异丙基苯)钌氯]螯合,合成了新型半夹心钌配合物[(对异丙基苯)RuClL],然后使用不同的光谱和分析技术对其进行了全面表征。配合物4的晶体结构表明,腙配体通过亚胺氮和咪唑酸酯氧以双齿方式与钌离子键合,呈现出以钌原子为中心的伪八面体几何结构。所制备的空气和水分稳定的半夹心钌配合物在温和条件下对酰肼的α-烷基化反应表现出优异的催化活性。在钌配合物的催化下,酰肼与不同类型的醇在一锅反应中发生反应,生成具有不同取代基的α-烷基化酰肼。该催化剂具有催化效率高、底物范围广、反应条件温和等特点,表明其在工业应用中具有巨大潜力。

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