Substituent Effects of β-Diketiminate Ligands on the Structure and Physicochemical Properties of Copper(II) Complexes
Substituent Effects of β-Diketiminate Ligands on the Structure and Physicochemical Properties of Copper(II) Complexes
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β-二酮亚胺配体的取代基对铜(II)配合物结构和理化性质的影响
DOI：
10.1021/ic0344766
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发表时间：
2003
影响因子：
4.6
通讯作者：
S. Itoh
中科院分区：
文献类型：
--
作者：
C. Shimokawa;S. Yokota;Y. Tachi;N. Nishiwaki;M. Ariga;S. Itoh
用3-亚氨基丙烯胺衍生物R1LR3H、R3NCHC(R1)CHNHR3，其中R1为Me、H、CN或NO2， R3为Ph、Mes（甲酰基）、Dep（2,6-二乙基苯基）、Dipp（2,6-二异丙基苯基）或Dtbp（3,5-二叔丁基苯基），系统地研究了β-二酮酸配体对铜（II）配合物结构和物理化学性质的取代效应。当R3 = Ph或Dtbp的配体用CuII(OAc)2处理时，得到了具有扭曲四面体几何形状的双（β-二酮酸）铜（II）配合物，无论α-取代基（R1）如何，其晶体结构几乎相同；两个β-二氯盐配位面之间的二面角为62.5±1.2°，Cu−N键长为1.959±0.008 A。溶液中保持了扭曲的四面体结构，但络合物的光谱特征，特别是ESR光谱的g∥值和吸收光谱的d - d波段，以及电化学行为都发生了变化。
Substituent effects of β-diketiminate ligands on the structure and physicochemical properties of the copper(II) complexes have been systematically investigated by using 3-iminopropenylamine derivatives R1LR3H, R3NCHC(R1)CHNHR3, where R1 is Me, H, CN, or NO2, and R3 is Ph, Mes (mesityl), Dep (2,6-diethylphenyl), Dipp (2,6-diisopropylphenyl), or Dtbp (3,5-di-tert-butylphenyl). When the ligands with R3 = Ph or Dtbp were treated with CuII(OAc)2, bis(β-diketiminate) copper(II) complexes exhibiting distorted tetrahedral geometries were obtained, the crystal structures of which were nearly the same as each other regardless of the α-substituent (R1); dihedral angles between the two β-diketiminate coordination planes are 62.5 ± 1.2°, and the Cu−N bond lengths are 1.959 ± 0.008 A. The distorted tetrahedral structures are maintained in solution, but the spectroscopic features, especially g∥ values of the ESR spectra and the d−d bands of the absorption spectra, as well as the electrochemical behaviors of the complexe...