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通过钌叠氮配合物与末端苯乙炔的[3 + 2]环加成反应直接合成N配位的钌4-芳基-1,2,3-三唑配合物以及结构中的非共价芳香相互作用。

The straightforward synthesis of N-coordinated ruthenium 4-aryl-1,2,3-triazolato complexes by [3 + 2] cycloaddition reactions of a ruthenium azido complex with terminal phenylacetylenes and non-covalent aromatic interactions in structures.

作者信息

Chang Chao-Wan, Lee Chi-Rung, Lee Gene-Hsiang, Lu Kuang-Lieh

机构信息

Division of Preparatory Programs for Overseas Chinese Students, National Taiwan Normal University Linkou New Taipei City 24449 Taiwan

Department of Applied Materials Science and Technology, Minghsin University of Science and Technology Hsinchu 30401 Taiwan.

出版信息

RSC Adv. 2022 Aug 31;12(38):24830-24838. doi: 10.1039/d2ra04835c. eCollection 2022 Aug 30.

Abstract

The straightforward preparation of N-coordinated ruthenium triazolato complexes by [3 + 2] cycloaddition reactions of a ruthenium azido complex [Ru]-N (1, [Ru] = (η-CH)(dppe)Ru, dppe = PhPCHCHPPh) with a series of terminal phenylacetylenes is reported. The reaction products, N(2)-bound ruthenium 4-aryl-1,2,3-triazolato complexes such as [Ru]NCH(4-CHCN) (2), [Ru]NCH(4-CHCHO) (3), [Ru]NCH(4-CHF) (4), [Ru]NCH(Ph) (5) and [Ru]NCH(4-CHCH) (6) were produced from 4-ethynylbenzonitrile, 4-ethynylbenzaldehyde, 1-ethynyl-4-fluorobenzene, phenylacetylene and 4-ethynyltoluene, respectively, at 80 °C or above under an atmosphere of air. To the best of our knowledge, this is the first example of the preparation of N-coordinated ruthenium aryl-substituted 1,2,3-triazolato complexes by the [3 + 2] cycloaddition of a metal-coordinated azido ligand and a terminal aryl acetylene, less electron-deficient terminal aryl alkynes. All of the compounds have been fully characterized and the structures of complexes 2, 3, 5 and 6 were confirmed by single-crystal X-ray diffraction analysis. Each compound participates in non-covalent aromatic interactions in the solid-state structure which can be favorable in the binding of DNA/biomolecular targets and has shown great potential in the development of biologically active anticancer drugs.

摘要

报道了通过钌叠氮配合物[Ru]-N(1,[Ru] = (η-CH)(dppe)Ru,dppe = PhPCHCHPPh)与一系列末端苯乙炔的[3 + 2]环加成反应直接制备N配位的钌三唑配合物。反应产物,即N(2)-键合的钌4-芳基-1,2,3-三唑配合物,如[Ru]NCH(4-CHCN)(2)、[Ru]NCH(4-CHCHO)(3)、[Ru]NCH(4-CHF)(4)、[Ru]NCH(Ph)(5)和[Ru]NCH(4-CHCH)(6),分别由4-乙炔基苯甲腈、4-乙炔基苯甲醛、1-乙炔基-4-氟苯、苯乙炔和4-乙炔基甲苯在80°C或更高温度下于空气气氛中制得。据我们所知,这是通过金属配位的叠氮配体与末端芳基乙炔(电子缺乏程度较低的末端芳基炔烃)的[3 + 2]环加成反应制备N配位的芳基取代钌1,2,3-三唑配合物的首个实例。所有化合物均已得到充分表征,配合物2、3、5和6的结构通过单晶X射线衍射分析得以确认。每种化合物在固态结构中都参与非共价芳香相互作用,这在DNA/生物分子靶点的结合中可能是有利的,并且在生物活性抗癌药物的开发中显示出巨大潜力。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/34c8/9430631/2546bdf1d219/d2ra04835c-f1.jpg

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