6-芳基取代三(2-吡啶基甲基)胺过渡金属配合物的结构与性质

Zhicong He, D. Craig, Stephen B. Colbran
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引用次数: 41

摘要

制备了一系列[6-(2′,5′-二甲氧基苯基)-2-吡啶基甲基]双(2-吡啶基甲基)胺的金属配合物。测定了L及其金属(II)氯化物配合物Mn、Fe、Co、Ni、Cu和Zn的x射线晶体结构,并对结果进行了比较。本文还介绍了不同寻常的碳酸盐桥接铜四聚体[Cu4(L)4(CO3)2][BF4]4·5.2H2O的制备和晶体结构。根据配合物的理化性质和光谱学性质推导出配合物的溶液态结构。Zn(II)配合物[ZnCl2(L)]在核磁共振时间标度上显示了配体胺基的反转-来自变温核磁共振研究的结果,并允许估计胺反转的阻挡为56±0.5 kJ mol−1。总的来说,研究发现,由单个6-芳基取代三(2-吡啶基甲基)胺(tpa)骨架所引入的分子内空间相互作用会导致所得到的金属配合物的结构和性质发生重大变化:特别是L中的芳基取代导致(i)与tpa相比,配体场较弱,有利于高自旋配合物,(ii)倾向于较低的配位数,以及(iii) Ni(ii)和Cu(ii)配合物的半半性-配体的芳基取代分支(L)是配位不稳定的。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Structures and properties of 6-aryl substituted tris(2-pyridylmethyl)amine transition metal complexes
A series of metal(II) complexes of [6-(2′,5′-dimethoxyphenyl)-2-pyridylmethyl]bis(2-pyridylmethyl)amine (L) have been prepared. X-Ray crystal structures have been determined for L and its metal(II) chloride complexes for Mn, Fe, Co, Ni, Cu and Zn and the results compared. The preparation and crystal structure of the unusual carbonato-bridged copper-tetramer [Cu4(L)4(CO3)2][BF4]4·5.2H2O is also described. The solution-state structures of the complexes are deduced from their physicochemical and spectroscopic properties. The Zn(II) complex, [ZnCl2(L)], shows inversion about the ligand amine group on the NMR timescale — results from a variable temperature NMR study are presented and allow estimation of the barrier to amine inversion as 56 ± 0.5 kJ mol−1. Overall, it is found that the intramolecular steric interactions introduced by substitution of the tris(2-pyridylmethyl)amine (tpa)-skeleton by a single 6-aryl group result in significant changes to the structures and properties of the resulting metal complexes: in particular the aryl-substitution in L causes (i) a weaker ligand-field compared to tpa favouring high-spin complexes, (ii) a tendency toward lower coordination numbers, and (iii) hemilability in the Ni(II) and Cu(II) complexes — the aryl-substituted leg of the ligand (L) is coordinatively labile.
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