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环金属化半夹心铱(III)配合物:以空气为氧化剂在亚胺合成中的合成、结构及多样催化活性

Cyclometalated Half-Sandwich Iridium(III) Complexes: Synthesis, Structure, and Diverse Catalytic Activity in Imine Synthesis Using Air as the Oxidant.

作者信息

Li Rong-Jian, Ling Chun, Lv Wen-Rui, Deng Wei, Yao Zi-Jian

机构信息

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

Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China.

出版信息

Inorg Chem. 2021 Apr 5;60(7):5153-5162. doi: 10.1021/acs.inorgchem.1c00174. Epub 2021 Mar 24.

Abstract

Four air-stable cyclometalated half-sandwich iridium complexes - with C,N-donor Schiff base ligands were prepared through C-H activation in moderate-to-good yields. These complexes have been well characterized, and their exact structure was elaborated on by single-crystal X-ray analysis. The iridium(III) complexes - showed good catalytic activity in the imine synthesis under open-flask conditions (air as the oxidant) from primary amine oxidative homocoupling, secondary amine dehydrogenation, and the cross-coupling reaction of amine and alcohol. Substituents bonded on the ligands of the iridium complexes displayed little effect on the catalytic efficiency. The stability and good catalytic efficiency of the iridium catalysts, mild reaction conditions, and substrate universality showed their potential application in industrial production.

摘要

通过C-H活化制备了四种具有空气稳定性的环金属化半夹心铱配合物——带有C,N-供体席夫碱配体,产率适中至良好。这些配合物已得到充分表征,并通过单晶X射线分析详细阐述了它们的确切结构。铱(III)配合物在开放烧瓶条件下(以空气作为氧化剂)由伯胺氧化均偶联、仲胺脱氢以及胺与醇的交叉偶联反应合成亚胺的过程中表现出良好的催化活性。连接在铱配合物配体上的取代基对催化效率影响很小。铱催化剂的稳定性和良好的催化效率、温和的反应条件以及底物通用性表明了它们在工业生产中的潜在应用。

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