首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >Reactivity of copper(I) complexes with tripodal ligands towards O-2: Structures of a precursor [(LCuI)-Cu-3(NCCH3)](BF4), L-3 = tris(3-isopropyl-4,5-trimethylenepyrazolyl)methane and of its oxidation product ((LCuII)-Cu-3(mu-OH)(2)(CuL3)-L-II](BF4)(2
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Reactivity of copper(I) complexes with tripodal ligands towards O-2: Structures of a precursor [(LCuI)-Cu-3(NCCH3)](BF4), L-3 = tris(3-isopropyl-4,5-trimethylenepyrazolyl)methane and of its oxidation product ((LCuII)-Cu-3(mu-OH)(2)(CuL3)-L-II](BF4)(2

机译:具有三脚架配体的铜(I)配合物对O-2的反应活性:前体[(LCuI)-Cu-3(NCCH3)](BF4)的结构,L-3 =三(3-异丙基-4,5-三亚甲基吡唑基)及其氧化产物((LCuII)-Cu-3(mu-OH)(2)(CuL3)-L-II](BF4)(2

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摘要

The molecular structure of the highly oxygen-sensitive complex [(LCu1)-Cu-3(NCCH3)](BF4) (1) reveals approximately symmetrical coordination by the fac-tridentate (tripodal) ligand L-3 = tris(3-isopropyl-4,5-trimethylenepyrazolyl)methane and a rather short Cu-I-N(acetonitrile) distance of 1.865(5) angstrom. In CH2Cl2 at -78 degrees C the colourless compound reacts with O-2 to yield a labile purple intermediate (gimel(max) 517 nm) - presumably a peroxodicopper(II) complex - which decomposes at -30 degrees C. No such intermediate was observed on reaction of the Cu-I complex of bis(2-pyridylmethyl)benzylamine with O-2 at - 80 degrees C. However, an EPR spectrum with g(parallel to) = 2.17 and g(perpendicular to) = 2.03 without Cu-63.65 hyperfine splitting was observed at low temperatures. Exposure of the precursor 1 to air under ambient conditions yields dinuclear [(LCuII)-Cu-3(mu-OH)(2-)(CuL3)-L-II](BF4)(2) (2) which exhibits an EPR detectable dissociation into monomers in CH,C], solution. The structure of the hexakis(dichloromethane) solvate of 2 with Cu-Cu and Cu-O distances of 3.055 and 1.94 angstrom, respectively, is typical for dihydroxo-bridged dicopper compounds with square-pyramidal Cu-II configuration (tau = 0.03), adopting an anti arrangement. In agreement with the relatively wide Cu-O-Cu angles of 103.5 degrees an analysis of the temperature dependence of the magnetic susceptibility revealed a rather strong (J = -633 cm(-1)) antiparallel spin-spin coupling. The effect is ascribed to the steric bulk of the ligand L-3.
机译:高氧敏感性复合物[(LCu1)-Cu-3(NCCH3)](BF4)(1)的分子结构显示出由三齿(三脚架)配体L-3 =三(3-异丙基)近似对称配位-4,5-三亚甲基吡唑基)甲烷和相当短的Cu-IN(乙腈)距离为1.865(5)埃。在-78℃的CH2Cl2中,无色化合物与O-2反应生成不稳定的紫色中间体(gimel(最大)517 nm)-可能是过氧二铜(II)配合物-在-30℃时分解。在-80℃下观察到双(2-吡啶基甲基)苄胺的Cu-I配合物与O-2的反应。但是,在没有Cu的情况下,具有g(平行)= 2.17和g(垂直于)= 2.03的EPR光谱在低温下观察到-63.65超细分裂。在环境条件下将前体1暴露在空气中会产生双核[(LCuII)-Cu-3(mu-OH)(2-)(CuL3)-L-II](BF4)(2)(2),具有EPR在CH,C]溶液中可检测解离为单体。 Cu-Cu和Cu-O距离分别为3.055和1.94埃的2的六(二氯甲烷)溶剂化物的结构通常是方形金字塔形Cu-II构型(tau = 0.03)的二氢桥联双铜化合物,采取反安排。与103.5度的相对较宽的Cu-O-Cu角相符,对磁化率的温度依赖性的分析显示出相当强的(J = -633 cm(-1))反平行自旋耦合。该作用归因于配体L-3的空间体积。

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