A complete series of copper(II) halide complexes (X = F, Cl, Br, I) with a novel Cu(II)-C(sp3) bond
A complete series of copper(II) halide complexes (X = F, Cl, Br, I) with a novel Cu(II)-C(sp3) bond
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DOI：
10.1039/b507073b
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发表时间：
2005-01-01
影响因子：
4
通讯作者：
Kinoshita, I
中科院分区：
文献类型：
--
作者：
Miyamoto, R;Santo, R;Kinoshita, I
完整系列的卤化铜（II）配合物[CuX（tptm）]（X = F（1），Cl（2），Br（3），I（4）; tptm = tris通过[Cu（tptm）（CH_3CN）] PF_6反应合成了一种新的具有Cu-II - C（sp（3））键的化合物（2-吡啶硫基）甲基（5中心点PF_6）与KF或n-Bu_4 NX（X = Cl，Br，I）的相应卤化物源反应，合成的三元双锥晶体结构已被X射线晶体学和/或EPR谱所证实。碘络合物4容易释放乙腈中的碘阴离子，结果形成乙腈络合物5。配合物的EPR谱显示了几种超超精细结构，这强烈表明通过Cu-X键在卤化物配体上存在自旋密度。DFT计算结果与X射线晶体学和EPR谱结果基本一致。循环伏安法显示了一个准可逆的还原波的Cu-II/Cu-I表明三角锥配位的Cu-I状态。所有[CuX（tptm）]（0/+）过程的氧化还原电位的重合表明每个络合物中的主要氧化位点是tptm配体。
A complete series of copper(II) halide complexes [CuX(tptm)] (X = F (1), Cl (2), Br (3), I (4); tptm = tris(2-pyridylthio) methyl) with a novel Cu-II - C(sp(3)) bond has been prepared by the reactions of [Cu(tptm)(CH3CN)] PF6 ( 5 center dot PF6) with corresponding halide sources of KF or n-Bu4NX (X = Cl, Br, I), and the trigonal bipyramidal structures have been confirmed by X-ray crystallography and/or EPR spectroscopy. The iodide complex 4 easily liberates the iodide anion in acetonitrile forming the acetonitrile complex 5 as a result. The EPR spectra of the complexes showed several superhyperfine structures that strongly indicated the presence of spin density on the halide ligands through the Cu - X bond. The results of DFT calculations essentially matched with the X-ray crystallographic and the EPR spectroscopic results. Cyclic voltammetry revealed a quasi-reversible reduction wave for Cu-II/Cu-I indicating a trigonal pyramidal coordination for Cu-I states. A coincidence of the redox potential for all [CuX(tptm)](0/+) processes indicates that the main oxidation site in each complex is the tptm ligand.