화학공학소재연구정보센터
Inorganic Chemistry, Vol.40, No.27, 7003-7008, 2001
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
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.