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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >(N-Benzyl-bis-N',N'-salicylidene)-cis-1,3,5-triaminocyclohexane copper(II):a novel catalyst for the aerobic oxidation of benzyl alcohol
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(N-Benzyl-bis-N',N'-salicylidene)-cis-1,3,5-triaminocyclohexane copper(II):a novel catalyst for the aerobic oxidation of benzyl alcohol

机译：（N-苄基-双-N'，N“-亚水杨基）-顺-1,3,5-三氨基环己烷铜（II）：一种新型好氧氧化苯甲醇的催化剂

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Reaction of Cu(BF_4)_2-6H_2O with the N_3O_2 donor ligand H_2L(where H_2L = N-benzyl-N',N"-di-tert-butyl-disalicyl-triaminocyclohexane)results in the formation of a novel Cu~(II)L complex,1.X-Ray crystallography of 1 shows the Cu~(II)centre coordinated by two phenolate oxygens and two imine nitrogens in a distorted square plane with an elongated bond to the amine nitrogen(2.512 A)in the axial position.EPR spectroscopy of 1 gives g values of g_1 =2.277,g_2 = 2.100,g_3 = 2.025,and A_1 = 15.6 mT which are consistent with the distorted square pyramidal coordination environment determined from the X-ray structure.UV/visible and electrochemical analysis of 1 shows that it undergoes two reversible processes assigned to the successive oxidation of the phenolate oxygens to phenoxyl radicals,the first at E_(1/2)= 0.89 V(DELTA E = 81 mV,vs.Ag/AgCl)and the second at E_(1/2)= 1.13V(DELTA E = 84 mV,vs.Ag/AgCl).Chemical oxidation of 1 results in the formation of a species,assigned as [1]~(+ centre dot)which is EPR silent due to antiferromagnetic coupling between the Cu~(II)centre and the bound phenoxyl radical.The oxidised species catalyses the oxidation of benzyl alcohol to benzaldehyde.
机译：Cu（BF_4）_2-6H_2O与N_3O_2供体配体H_2L（其中H_2L = N-苄基-N'，N“-二叔丁基-二水杨基-三氨基环己烷）的反应导致形成新的Cu〜（II L络合物，1.X射线晶体学显示1的Cu〜（II）中心在扭曲的方平面中由两个酚盐氧和两个亚胺氮配位，在轴向位置上与胺氮（2.512 A）呈细长键.EPR光谱1的g值为g_1 = 2.277，g_2 = 2.100，g_3 = 2.025，A_1 = 15.6 mT，这与从X射线结构确定的扭曲的方形金字塔配位环境一致.UV /可见光和电化学分析1的曲线表明它经历了两个可逆过程，分别被酚醛酸氧连续氧化为苯氧基，第一个在E_（1/2）= 0.89 V（DELTA E = 81 mV，vs.Ag / AgCl）下进行，第二个在E_（1/2）= 1.13V（DELTA E = 84 mV，vs.Ag / AgCl）.1的化学氧化导致形成物种，指定为[1]〜（+ center do由于Cu〜（II）中心与结合的苯氧基自由基之间存在反铁磁耦合，因此EPR是沉默的。氧化的物质催化苄醇氧化为苯甲醛。

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