Structure-spectroscopy correlation in distorted five-coordinate Cu(II) complexes: A case study with a set of closely related copper complexes of pyridine-2,6-dicarboxamide ligands
Structure-spectroscopy correlation in distorted five-coordinate Cu(II) complexes: A case study with a set of closely related copper complexes of pyridine-2,6-dicarboxamide ligands
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DOI：
10.1021/ic010523n
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发表时间：
2001-12-31
影响因子：
4.6
通讯作者：
Mascharak, PK
中科院分区：
文献类型：
--
作者：
Marlin, DS;Olmstead, MM;Mascharak, PK
以[Cu（dmppy）]（dmppyH（2）=三齿配体N，N '-二甲基吡啶-2，6-二甲酰胺; H是可离解的酰胺质子）和吡啶、水、N-甲基咪唑、取代和未取代邻菲咯啉、联吡啶等配体合成了8个Cu（II）配合物，并对其结构进行了表征。这些结构相关的五配位Cu（II）配合物（和两个以前报道的）的底角相关以及EPR超精细分裂参数所有。然而，参数τ的值，它提供了一个衡量的程度的正方形金字塔与三角双锥几何形状所采用的这些复合物不与所有的值线性相关。很明显，面外畸变和配体应变使得在某些五配位Cu（H）配合物中τ的计算不一致。在这种情况下，涉及tau的结构光谱相关性是不可行的。
Eight Cu(II) complexes with the [Cu(dmppy)] moiety (dmppyH(2) = tridentate ligand N,N'-dimethylpyridine-2,6dicarboxamide; H's are dissociable amide protons) and ligands like pyridine, water, N-methylimidazole, substituted and unsubstituted o-phenanthroline, and bipyridine have been isolated and structurally characterized. The basal angles of these structurally related five-coordinate Cu(II) complexes (and two previously reported ones) correlate well with the EPR hyperfine splitting parameter All. However, the values of the parameter tau which provides a measure of the degree of square pyramid versus trigonal bipyramid geometry adopted by these complexes do not correlate linearly with the All values. It is evident that out-of-plane distortions and ligand strain make calculation of tau inconsistent in certain sets of five-coordinate Cu(H) complexes. Structure-spectroscopy correlation involving tau is not feasible in such cases.