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含NO双齿配体的钌配合物的合成、光谱及催化脱氢研究

Synthesis, spectral and catalytic dehydrogenation studies of ruthenium complexes containing NO bidentate ligands.

作者信息

Shoair A F, El-Bindary A A

机构信息

Chemistry Department, Faculty of Science, Damietta University, 34517 Damietta, Egypt.

Chemistry Department, Faculty of Science, Damietta University, 34517 Damietta, Egypt.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2014 Oct 15;131:490-6. doi: 10.1016/j.saa.2014.04.132. Epub 2014 Apr 30.

Abstract

The synthesis and characterization of ruthenium mononuclear complexes containing NO bidentate ligands are reported. The complexes cis-Ru(II)(bpy)2Ln (1a-c), [Ru(III)Cl(L)2(H2O)] (2a-b) and [Ru(III)Cl2(L)2]Cl (2c) were prepared by the reaction of cis-[Ru(II)Cl2(bpy)2]·2H2O (bpy=2,2'-bipyridine) and/or RuCl3·nH2O with the Ligands: 2-aminophenol (2-aph), 8-hydroxyquinoline (8-hq) and 4-aminoantipyrine (4-apy). These complexes were characterized by elemental analysis, spectroscopic (IR, UV-Vis, (1)H NMR, ESR) and magnetic susceptibility measurements. The ligand field parameters, Δo (splitting parameter), B (Racah parameter of interelectronic repulsion), and β (nephelauxetic ratio) were calculated. The redox properties were also investigated electrochemically by cyclic voltammetry. The complexes cis-Ru(II)(bpy)2(8-hq)2 (1b) and [Ru(III)Cl(8-hq)2(H2O)] (2b) have been investigated in conjunction with N-methylmorpholine-N-oxide (NMO) as co-oxidant for the catalytic dehydrogenation of benzyl amine, p-methyl benzylamine and p-nitrobenzylamine to their respective nitriles.

摘要

报道了含NO双齿配体的钌单核配合物的合成与表征。配合物顺式-Ru(II)(bpy)₂Lₙ (1a - c)、[Ru(III)Cl(L)₂(H₂O)] (2a - b) 和 [Ru(III)Cl₂(L)₂]Cl (2c) 通过顺式-[Ru(II)Cl₂(bpy)₂]·2H₂O (bpy = 2,2'-联吡啶) 和/或RuCl₃·nH₂O 与配体:2-氨基苯酚 (2-aph)、8-羟基喹啉 (8-hq) 和4-氨基安替比林 (4-apy) 反应制备。通过元素分析、光谱学方法(红外光谱、紫外可见光谱、¹H NMR、电子自旋共振)和磁化率测量对这些配合物进行了表征。计算了配体场参数Δo(分裂参数)、B(电子间排斥的拉卡参数)和β(电子云扩展比)。还通过循环伏安法对氧化还原性质进行了电化学研究。研究了配合物顺式-Ru(II)(bpy)₂(8-hq)₂ (1b) 和 [Ru(III)Cl(8-hq)₂(H₂O)] (2b) 与N-甲基吗啉-N-氧化物 (NMO) 作为共氧化剂用于将苄胺、对甲基苄胺和对硝基苄胺催化脱氢为各自的腈。

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