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A cyclic tetranuclear cuboid type copper(II) complex doubly supported by cyclohexane-1,4-dicarboxylate: molecular and supramolecular structure and cyclohexane oxidation activity

机译:环己烷-1,4-二羧酸酯双重负载的环状四核长方体型铜(II)配合物:分子和超分子结构以及环己烷的氧化活性

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摘要

Synthesis, characterization and catalytic study of the new bis(mu(4)-(ae)-cyclohexane-1,4-dicarboxylato-O,O',O '',O''')-tetracopper(II) complex [(CuL)(2)(mu(4)-O,O ',O '',O'''-CDC)](2)center dot 2H(2)O (1) (HL = 2-(2-pyridylmethyleneamino)benzenesulfonic acid and CDC = cyclohexane-1,4-dicarboxylate) are described. Complex 1 contains four copper(II) centres connected by four Schiff base ligands (L-) and doubly bridged by two cyclohexane-1,4-dicarboxylate moieties. The axial-equatorial conformation of the carboxylate groups of CDC stabilizes a tetracopper di-CDC ring in a cuboid type fashion. Compound 1 is applied as an efficient pre-catalyst for the oxidation of cyclohexane by aqueous H2O2 under mild conditions (50 degrees C) in CH3CN/H2O medium. Without any promoter, a total yield (based on substrate) of cyclohexanol and cyclohexanone up to 35% was achieved.
机译:新型双(mu(4)-(ae)-环己烷-1,4-二羧基-O-O,O',O'',O''')-四铜(II)配合物的合成,表征和催化研究CuL)(2)(mu(4)-O,O',O'',O'''-CDC)](2)中心点2H(2)O(1)(HL = 2-(2-吡啶基亚甲基氨基描述了苯磺酸和CDC = 1,4-二羧酸环己烷)。配合物1包含通过四个席夫碱配体(L-)连接并通过两个环己烷-1,4-二羧酸酯部分双桥的四个铜(II)中心。 CDC的羧酸酯基的轴向-赤道构象以长方体类型的方式稳定了四铜双CDC环。在温和的条件下(50摄氏度),在CH3CN / H2O介质中,化合物1作为有效的预催化剂被H2O2水溶液氧化成环己烷。没有任何促进剂,环己醇和环己酮的总收率(基于底物)可达35%。

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