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首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >SYNTHESIS, X-RAY STRUCTURE AND PROPERTIES OF A NEW NITRITE-BOUND COPPER(II) COMPLEX WITH 2-(3,5-DIMETHYLPYRAZOL-1-YLMETHYL)PYRIDINE IN A CUN4(O) COORDINATION
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SYNTHESIS, X-RAY STRUCTURE AND PROPERTIES OF A NEW NITRITE-BOUND COPPER(II) COMPLEX WITH 2-(3,5-DIMETHYLPYRAZOL-1-YLMETHYL)PYRIDINE IN A CUN4(O) COORDINATION

机译：CUN4（O）配位的新型2-（3,5-二甲基吡唑-1-吡啶）吡啶亚硝化铜（II）络合物的合成，X射线结构和性质

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摘要

Synthesis and characterization of a nitrile-bound copper(II) compound [Cu(L-4)(2)(ONO)]ClO4 have been achieved (L-4 = 2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine]. The bidentate ligand L-4 provides a pyridine and a pyrazole donor site; however, they are separated by a methylene spacer. The complex has been structurally characterized and it belongs to only a handful of complexes having nitrito-bound mononuclear copper(II) centre. The metal atom has a distorted square pyramidal geometry with the copper atom displaced from the equatorial plane by 0.25 Angstrom. In MeCN solution the green complex exhibits a broad ligand-field transition at 655 nm with a shoulder at 675 nm and in dichloromethane-toluene glass (80 K) it exhibits an EPR spectral feature characteristic of the unpaired electron in the d(x)2-(y)2 orbital Variable-temperature (80-300 K) magnetic susceptibility measurements in the solid stale as well as room temperature measurement in MeCN solution reveal mononuclear magnetically dilute copper(II) centre. When examined by cyclic voltammetry (MeCN solution) it displays electrochemically irreversible Cu-II-Cu-I response [cathodic peak potential, E-pc (V vs saturated calomel electrode (SCE)): -0.32]. An oxidative response is observed at 1.14 V, probably due to bound-nitrite oxidation and is partially removed to generate a solvated complex at the electrode surface. The latter species gives rise to a reversible Cu-II-Cu-I redox response [E-1/2 = 0.41 V vs SCE]. (C) 1997 Elsevier Science Ltd. [References: 49]
机译：已实现腈键合铜（II）化合物[Cu（L-4）（2）（ONO）] ClO4的合成和表征（L-4 = 2-（3,5-二甲基吡唑-1-基甲基）吡啶二齿配体L-4提供吡啶和吡唑供体位点，但它们之间被亚甲基间隔基隔开，该配合物在结构上已得到表征，仅属于少数具有与腈基结合的单核铜的配合物（II）金属原子具有扭曲的方形金字塔形状，铜原子与赤道平面的距离为0.25埃，在MeCN溶液中，绿色络合物在655 nm处显示宽的配体场跃迁，在675 nm处出现肩峰，在二氯甲烷中-甲苯玻璃（80 K），它在d（x）2-（y）2轨道可变温度（80-300 K）磁化率测量中显示未配对电子的EPR光谱特征，以及MeCN溶液中的室温测量揭示了单核磁d稀铜（II）中心。当通过循环伏安法（MeCN溶液）检查时，它显示出电化学不可逆的Cu-II-Cu-I反应[阴极峰电位，E-pc（V对饱和甘汞电极（SCE））：-0.32]。在1.14 V处观察到氧化反应，这可能是由于键合亚硝酸盐的氧化所致，并且被部分去除以在电极表面产生溶剂化的络合物。后者会引起可逆的Cu-II-Cu-I氧化还原响应[E-1 / 2 = 0.41 V vs SCE]。 （C）1997 Elsevier Science Ltd. [参考：49]

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