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N-[二(苯基/乙基)氨甲酰硫代]苯甲酰胺单齿配位:Cu(I)配合物的合成、晶体结构和催化氧化性能。

Monodentate coordination of N-[di(phenyl/ethyl)carbamothioyl]benzamide ligands: synthesis, crystal structure and catalytic oxidation property of Cu(I) complexes.

机构信息

Department of Chemistry, National Institute of Technology, Tiruchirappalli, 620 015, India.

出版信息

Dalton Trans. 2011 Dec 14;40(46):12519-26. doi: 10.1039/c1dt10628g. Epub 2011 Oct 10.

Abstract

New four-coordinated tetrahedral copper(I) complexes have been synthesized from the reactions between [CuCl(2)(PPh(3))(2)] and N-(diphenylcarbamothioyl)benzamide (HL1) or N-(diethylcarbamothioyl)benzamide (HL2) in benzene. These complexes have been characterized by elemental analyses, IR, UV/Vis, (1)H, (13)C and (31)P NMR spectroscopy. The molecular structure of both the complexes, [CuCl(HL1)(2)(PPh(3))] (1) and [CuCl(HL2)(PPh(3))(2)] (2) were determined by single-crystal X-ray diffraction, which reveals distorted tetrahedral geometry around each Cu(I) ion. The combination of 2 (0.005 mmol) with hydrogen peroxide (2.5 mmol) in acetonitrile is found to be an active catalyst for the oxidation of primary and secondary alcohols (0.5 mmol) to their corresponding acids and ketones, respectively, at room temperature.

摘要

新型四配位四面体型铜(I)配合物由[CuCl(2)(PPh(3))(2)]与 N-(二苯氨基甲硫酰基)苯甲酰胺(HL1)或 N-(二乙氨基甲硫酰基)苯甲酰胺(HL2)在苯中反应得到。这些配合物通过元素分析、IR、UV/Vis、(1)H、(13)C 和 (31)P NMR 光谱进行了表征。配合物[CuCl(HL1)(2)(PPh(3))](1)和 [CuCl(HL2)(PPh(3))(2)](2)的分子结构通过单晶 X 射线衍射确定,结果表明每个 Cu(I)离子都呈现出扭曲的四面体型几何结构。在乙腈中,将 2(0.005 mmol)与过氧化氢(2.5 mmol)结合,在室温下发现其是一种有效的催化剂,可分别将一级和二级醇(0.5 mmol)氧化为相应的酸和酮。

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