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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Thermodynamic and kinetic studies on the Cu~(2+)coordination chemistry of a novel binucleating pyridinophane ligand
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Thermodynamic and kinetic studies on the Cu~(2+)coordination chemistry of a novel binucleating pyridinophane ligand

机译:新型双核吡啶并吡啶配体的Cu〜(2+)配位化学的热力学和动力学研究

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摘要

The synthesis and coordination chemistry of the novel pyridine-functionalized ligand 2,6,9,12,16-pentaaza[17]-(2,6)pyridinophane(L~1)is described.The compound behaves as a hexaprotic base in aqueous solution.NMR studies indicate a protonation pattern in which the sp2 pyridine nitrogen(N(py))does not undergo a net protonation although it is involved in formation of hydrogen bonds.L~1 forms mono and binuclear hydroxylated complexes.The crystal structure of [CuL~1](ClO_4)_2 shows a square planar coordination for Cu~(2+)with the pyridine and the three central nitrogens of the chain forming the vertices of the square.The benzylic nitrogens could be occupying the axial positions of a strongly axially asymmetrically elongated octahedron.The kinetic data show that decomposition of the [Cu(HL~1)]~(3+),[CXL~1)]~(2+)and [Cu_2(L~1)(OH)]~(3+)complexes takes place in two steps the slower one being ascribed to the dissociation of the Cu-N(py)bond.
机译:描述了新型的吡啶官能化配体2,6,9,12,16-五氮杂[17]-(2,6)吡啶oph(L〜1)的合成和配位化学。 NMR研究表明质子化模式,其中sp2吡啶氮(N(py))虽然参与氢键的形成但不经历净质子化.L〜1形成单核和双核羟基化配合物。 [CuL〜1](ClO_4)_2显示Cu〜(2+)的正方形平面配位,吡啶和链中的三个中心氮形成正方形的顶点。苄基氮可能占据a的轴向位置动力学数据表明,[Cu(HL〜1)]〜(3 +),[CXL〜1)]〜(2+)和[Cu_2(L〜1)(OH)分解]〜(3+)络合物发生在两个步骤中,较慢的一个归因于Cu-N(py)键的解离。

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