کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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1310283 | 975239 | 2008 | 7 صفحه PDF | دانلود رایگان |
The synthesis of an unsymmetrical phenanthroline-based ligand, 2-methyl-9-(3,5-dimethylpyrazolylmethyl)-1,10-phenanthroline (L), and its cupric [Cu(II)] (1) and cuprous [Cu(I)] (2) complexes, are reported. The X-ray structures of each of these Cu complexes show distinct changes in coordination environments consistent with the geometrical preferences of the two oxidation states. In the solid-state, the Cu(II) complex (1) adopts a geometry best described as trigonal bipyramidal, while the Cu(I) complex (2) consists of a single dicationic dimer in which the ligand bridges between two copper ions, separated by 4.26 Å. The two Cu(I) coordination sites differ in 2 with one copper center complexed in a trigonal planar geometry and the other copper in a distorted tetrahedral environment; the latter coordination results from an additional CH3CN ligand. Complex 1 exhibits a reversible redox process at −0.34 V versus Fc/Fc+ in CH3CN, attributable to the Cu2+/Cu+ couple, while the dimeric Cu(I) complex (2) does not display this redox couple on the CV timescale. Over minutes however, complex 1 does oxidize in the presence of dioxygen to 2 in CH3CN.
The synthesis of a tridentate ligand integrating both phenanthroline and 3,5-dimethylpyrazolyl moieties is presented along with its Cu(I) and Cu(II) structures. In the solid-state, the Cu(II) complex adopts a geometry best described as trigonal bipyramidal, while the Cu(I) complex consists of a single dicationic dimer in which the ligand bridges between two copper ions, separated by 4.26 Å. The Cu(I) complex slowly oxidizes in the presence of dioxygen.Figure optionsDownload as PowerPoint slide
Journal: Inorganica Chimica Acta - Volume 361, Issue 4, 3 March 2008, Pages 1142–1148