Steric-influenced fluxionality in monomeric two and three coordinate copper(I) complexes with a trans-chelating bis-pyrazole ligand

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• 作者：Chang-Chuan Chou^a ; ^{ccchou@mail.cgust.edu.tw} ; Hsueh-Ju Liu^a ; Lucas Hung-Chieh Chao^a ; Hong-Bin Syu^a ; Ting-Shen Kuo^b
• 关键词：Copper(I) ; Two coordinate ; Three coordinate ; Fluxionality ; Steric effect ; Trans-chelating ligand
• 刊名：Polyhedron
• 出版年：2012
• 期刊代码：87_02775387
• 类别：ch
• 出版时间：23 April, 2012
• 卷：37
• 期：1
• 页码：60-65
• 文件大小：664 K

摘要

Two new trans-chelating bispyrazolyl ligands, L^H, where L^H = 1,3-bis-(3,5-dimethyl-pyrazol-1-ylmethyl)-2,3-dihydro-1H-perimidine, and , where , and their two and three coordinate copper(I) derivatives [Cu(L^H)](ClO₄) (3路ClO₄), (4路ClO₄), and [Cu(L^H)I] (5) were prepared and structurally characterized by X-ray crystallography. The variable-temperature ¹H NMR spectra showed that complex 4路ClO₄ is rigid, whereas complexes 3路ClO₄ and 5 are nonrigid in CH₂Cl₂ solution. This suggests that the steric bulk of the 2-substituents in the dihydroperimidine moiety could impart some steric effects upon the fluxional behavior of individual two and three coordinate copper(I)-pyrazole complexes, in comparison with the rigid three coordinate copper(I) complex [Cu(L^Ph)I] (2) and dynamic two coordinate copper(I) complex [Cu(L^Ph)](ClO₄) (1路ClO₄) found previously . To the best of our knowledge, complex 5 represents the first example of a dynamic monomeric three coordinate copper(I) complex.