A stereodynamic tripodal ligand with three different coordinating arms: synthesis and zinc(II), copper(I) complexation study.
A stereodynamic tripodal ligand with three different coordinating arms: synthesis and zinc(II), copper(I) complexation study.
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DOI：
10.1002/chir.20833
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发表时间：
2011-01
期刊：
影响因子：
2
通讯作者：
Canary, James W.
中科院分区：
文献类型：
--
作者：
Liang, Jian;Canary, James W.
设计并合成了一个含有一个手性中心和三个不同配位臂的四齿三脚架配体。通过核磁共振和光谱研究了它与ZnII和CuI的络合性能。NMR实验证明了两种非对映异构体的形成，表明通过金属配位稳定了中心叔胺构型。发现配体的中心叔胺的反硝化作用高度依赖于金属离子、溶剂和温度。动态NMR测量用于估计氮原子反转所需的活化能。最后，吸收和圆二色性测量证实了预期的金属配合物的配位体引起圆二色性，但这种光谱的特征不在于激子耦合，与先前描述的配位体含有两个相同的臂与强发色团。
A tetradentate tripodal ligand containing a chiral center and three different coordinating arms was designed and synthesized. Its complexation properties with ZnII and CuI were studied by NMR and optical spectroscopy. NMR experiments demonstrated the formation of two diastereomers, indicating the stabilization of the central tertiary amine configuration by metal coordination. The inversion of pyramidalization of the central tertiary amine of the ligand was found to be highly dependent upon metal ion, solvent, and temperature. Dynamic NMR measurements were used to estimate the energy of activation required for nitrogen atom inversion. Finally, absorption and circular dichroism measurements confirmed the expectation that metal complexes of the ligand gave rise to circular dichroism but that such spectra were not characterized by exciton-coupling, in contrast to previously described ligands containing two identical arms with strong chromophores.
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