Synthesis, Characterization and Copper Chemistry of a Non-symmetric Ligand: 2-Methyl-9-(3,5-dimethyl-N-pyrazolylmethyl)-1,10-phenanthroline.
Synthesis, Characterization and Copper Chemistry of a Non-symmetric Ligand: 2-Methyl-9-(3,5-dimethyl-N-pyrazolylmethyl)-1,10-phenanthroline.
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非对称配体的合成、表征和铜化学：2-甲基-9-(3,5-二甲基-N-吡唑基甲基)-1,10-菲咯啉。
DOI：
10.1016/j.ica.2007.09.016
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发表时间：
2008
影响因子：
2.8
通讯作者：
Stack,TDanielP
中科院分区：
文献类型：
--
作者：
Masood,MdAthar;Storr,Tim;Stack,TDanielP
报道了一种不对称的邻菲咯啉配体2-甲基-9-（3，5-二甲基吡唑甲基）-1，10-邻菲咯啉（L）及其铜[Cu（II）]（1）和亚铜[Cu（I）]（2）配合物的合成。这些铜配合物的X-射线结构显示出不同的变化，在协调环境中的两个氧化态的几何偏好一致。在固态下，Cu（II）配合物（1）采用最佳描述为三角双锥的几何结构，而Cu（I）配合物（2）由单个双阳离子二聚体组成，其中配体桥接在两个铜离子之间，相隔4.26 μ m。两个Cu（I）配位位点的不同之处在于2，其中一个铜中心以三角平面几何形状络合，另一个铜中心以扭曲四面体环境络合;后者的配位结果来自额外的CH 3CN配体。配合物1在-0.34V处相对于Fc/Fc+在CH 3CN中表现出可逆的氧化还原过程，归因于Cu 2 +/Cu+电对，而二聚Cu（I）配合物（2）在CV时间尺度上不显示这种氧化还原电对。然而，在几分钟内，络合物1在分子氧的存在下在CH 3CN中氧化成2。
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 4.26Å. 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 −0.34V 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.