Gas, solution, and solid state coordination environments for the nickel(II) complexes of a series of aminopyridine ligands of varying coordination number
Gas, solution, and solid state coordination environments for the nickel(II) complexes of a series of aminopyridine ligands of varying coordination number
复制标题
一系列不同配位数的氨基吡啶配体的镍(II)配合物的气体、溶液和固态配位环境
DOI：
10.1016/s0020-1693(99)00288-1
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发表时间：
2000
影响因子：
2.8
通讯作者：
J. Callahan
中科院分区：
文献类型：
--
作者：
J. R. Hartman;R. Vachet;J. Callahan
描述了由一系列从三齿到七齿的氨基吡啶配体合成和表征镍(II)配合物。配体包括三脚配体三(2-((2-吡啶基甲基)氨基)乙基)胺，TREN-pyr和以下线性配体：(2-吡啶基甲基)(2-(2-((2-((2-吡啶基甲基)氨基)乙基)氨基)乙基)胺，TRIEN-pyr；双(2-((2-吡啶基甲基)氨基)乙基)胺，DIEN-pyr； (2-吡啶基甲基)(2-((2-吡啶基甲基)氨基)乙基)胺，EN-pyr；双(2-吡啶基甲基)胺，AM-pyr；和甲基(2-((-吡啶基甲基)氨基)乙基)胺，MeEN-pyr 使用以下方法确定镍(II)络合物在固相、溶液和气相中的结合几何形状：磁化率测量、吸收光谱、电化学和分析。质谱仪中的气相离子分子反应。线性配体的连接五元螯合特征似乎对凝聚相中的配合物施加了高自旋、八面体几何形状。三脚配体 TREN-pyr 和两个三齿配体 AM-pyr 和 MeEN-pyr 在气相中形成六配位配合物。 DIEN-pyr 和 EN-pyr）被发现在气相中具有较低的配位数（分别为五配位、五配位和四配位）。潜在的七齿三脚配体 TREN-pyr 似乎并未赋予溶液或固相中的 Ni(II) 离子任何不寻常的性质，但在气相中维持六配位几何形状方面似乎比六配位体 TRIEN-pyr 更有效。
The synthesis and characterization of the nickel(II) complexes from a series of aminopyridine ligands that range from tri- to heptadentate is described. The ligands include the tripod ligand tris(2-((2-pyridylmethyl)amino)ethyl)amine, TREN-pyr, and the following linear ligands: (2-pyridylmethyl)(2-(2-((2-((2-pyridylmethyl)amino)ethyl)amino)ethyl)amine, TRIEN-pyr; bis(2-((2-pyridylmethyl)amino)ethyl)amine, DIEN-pyr; (2-pyridylmethyl)(2-((2-pyridylmethyl)amino)ethyl)amine, EN-pyr; bis(2-pyridylmethyl)amine, AM-pyr; and methyl(2-((-pyridylmethyl)amino)ethyl)amine, MeEN-pyr. The following methods were used to determine the binding geometries of the nickel(II) complexes in the solid, solution, and gas phases: magnetic susceptibility measurements, absorption spectroscopy, electrochemistry, and analyzing the gas phase ion-molecule reactions in a mass spectrometer. The linked five-membered chelate character of the linear ligands appear to have imposed high-spin, octahedral geometry on the complexes in the condensed phases. The tripod ligand TREN-pyr and the two tridentate ligands, AM-pyr and MeEN-pyr, form six-coordinate complexes in the gas phase. In contrast, the rest of the complexes (TRIEN-pyr, DIEN-pyr, and EN-pyr) were found to have lower coordination numbers in the gas phase (five-, five-, and four-coordinate, respectively). The potentially heptadentate tripod ligand TREN-pyr does not appear to confer any unusual properties on the Ni(II) ion in the solution or solid phases, but does appear to be more effective than the hexadentate ligand TRIEN-pyr at maintaining the six-coordinate geometry in the gas phase.