Tetrahedral Copper(II) Complexes with a Labile Coordination Site Supported by a tris-Tetramethylguanidinato Ligand
Tetrahedral Copper(II) Complexes with a Labile Coordination Site Supported by a tris-Tetramethylguanidinato Ligand
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三四甲基胍配体支持的具有不稳定配位位点的四面体铜 (II) 配合物
DOI：
10.1021/acs.inorgchem.7b01154
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发表时间：
2017
期刊：
影响因子：
4.6
通讯作者：
Peter Comba,* and Shinobu Itoh*
中科院分区：
文献类型：
--
作者：
Ikuma Shimizu;Yuma Morimoto;Dieter Faltermeier;Marion Kerscher;Sayantan Paria;Tsukasa Abe;Hideki Sugimoto;Nobutaka Fujieda;Kaori Asano;Takeyuki Suzuki;Peter Comba,* and Shinobu Itoh*
开发了一种由顺式，顺式1,3,5-三氨基环己烷（tach）和三个N,N,N',N'-四甲基胍（TMG）基团组成的新型三齿N3配体（TMG3tach），用于制备具有四面体几何形状和不稳定配位位点的铜配合物。用 CuIIX2(X = Cl 和 Br) 处理配体得到卤化铜 (II) 配合物 [CuII(TMG3tach)Cl]+(2Cl) 和 [CuII(TMG3tach)Br]+(2Br)，其结构已通过 X 射线晶体学分析确定。该配合物表现出具有C3v对称性的四配位结构，其中不稳定的卤化物配体(X)占据三角轴上的位置。2Br通过用等摩尔量的氢氧化四丁基铵的甲醇溶液处理，转化为甲氧基铜(II)配合物[CuII(TMG3tach)(OMe)](OTf)(2OMe)，也具有类似的四配位几何结构。通过分别与中性苯酚和苯硫酚衍生物的配体交换反应，甲氧基络合物2OM进一步转化为相应的酚酸铜(II) (2OAr)和苯硫酚酸铜(II) (2SAr)络合物。基于EPR光谱和DFT计算，讨论了具有不同轴向配体的铜(II)配合物的电子结构。
A new tridentate N3ligand (TMG3tach) consisting ofcis,cis-1,3,5-triaminocyclohexane (tach) and threeN,N,N′,N′-tetramethylguanidino (TMG) groups has been developed to prepare copper complexes with atetrahedralgeometry and a labile coordination site. Treatment of the ligand with CuIIX2(X = Cl and Br) gave copper(II)-halide complexes, [CuII(TMG3tach)Cl]+(2Cl) and [CuII(TMG3tach)Br]+(2Br), the structures of which have been determined by X-ray crystallographic analysis. The complexes exhibit a four-coordinate structure withC3vsymmetry, where the labile halide ligand (X) occupies a position on the trigonal axis.2Brwas converted to a methoxido-copper(II) complex [CuII(TMG3tach)(OMe)](OTf) (2OMe), also having a similar four-coordinate geometry, by treating it with an equimolar amount of tetrabutylammonium hydroxide in methanol. The methoxido-complex2OMewas further converted to the corresponding phenolato-copper(II) (2OAr) and thiophenolato-copper(II) (2SAr) complexes by ligand exchange reactions with the neutral phenol and thiophenol derivatives, respectively. The electronic structures of the copper(II) complexes with different axial ligands are discussed on the basis of EPR spectroscopy and DFT calculations.