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含N(4)O(4)供体的双核钌(III)席夫碱配合物及其对醇的催化氧化作用

Binuclear ruthenium(III) Schiff base complexes bearing N(4)O(4) donors and their catalytic oxidation of alcohols.

作者信息

Venkatachalam G, Raja N, Pandiarajan D, Ramesh R

机构信息

School of Chemistry, Bharathidasan University, Tiruchirappalli 620 024, India.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2008 Dec 1;71(3):884-91. doi: 10.1016/j.saa.2008.02.006. Epub 2008 Feb 12.

Abstract

An interesting series of binuclear ruthenium(III) Schiff base complexes bearing bis-salophen/bis-naphophen units of the general composition [(EPh(3))(X)Ru-L-Ru(X)(EPh(3))] (where E=P or As; X=Cl or Br; L=binucleating dianionic tetradentate ligands) have been synthesized and characterized by analytical (elemental analysis, magnetic susceptibility measurements), spectral (FT-IR, UV-vis and EPR) and electrochemical methods. These ruthenium(III) complexes have two N(2)O(2) metal binding sites, which are linked to each other with a biphenyl bridge and acts as potential catalyst for oxidation of wide range of primary and secondary alcohols to corresponding aldehydes or ketones with moderate to high conversion in the presence of N-methylmorpholine-N-oxide (NMO). The formation of high-valent Ru(V)=O species as a catalytic active intermediate is proposed for the catalytic processes.

摘要

合成了一系列有趣的双核钌(III)席夫碱配合物,其带有通式为[(EPh(3))(X)Ru-L-Ru(X)(EPh(3))]的双水杨醛缩邻苯二胺/双萘酚单元(其中E = P或As;X = Cl或Br;L = 双核二价阴离子四齿配体),并通过分析方法(元素分析、磁化率测量)、光谱方法(傅里叶变换红外光谱、紫外可见光谱和电子顺磁共振光谱)以及电化学方法对其进行了表征。这些钌(III)配合物具有两个N(2)O(2)金属结合位点,它们通过联苯桥相互连接,并在N-甲基吗啉-N-氧化物(NMO)存在下作为潜在催化剂,将多种伯醇和仲醇氧化为相应的醛或酮,转化率适中至高。催化过程中提出形成高价Ru(V)=O物种作为催化活性中间体。

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