Synthesis, spectroscopic properties and X-ray crystal structures of two dinuclear alkoxo-bridged copper(II) compounds with the ligand bis(1-methyl-2-benzimidazolyl) propane. A unique alkoxo-bridged Cu(II) dinuclear compound with an additional bidentate bridging triflate anion
Synthesis, spectroscopic properties and X-ray crystal structures of two dinuclear alkoxo-bridged copper(II) compounds with the ligand bis(1-methyl-2-benzimidazolyl) propane. A unique alkoxo-bridged Cu(II) dinuclear compound with an additional bidentate bridging triflate anion
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DOI：
10.1016/s0020-1693(96)05554-5
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发表时间：
1997-07-30
影响因子：
2.8
通讯作者：
Reedijk, J
中科院分区：
文献类型：
--
作者：
vanAlbada, GA;Smeets, WJJ;Reedijk, J
以新配体双（1-甲基-2-苯并咪唑基）丙烷（简称MTBZ）为配体，合成了几种新的铜（II）配合物，并对其进行了结构和光谱表征。用X射线衍射法对两个典型化合物[Cu-2（mtbz）（2）（CH 3 O）（2）（CF 3SO 3）]（CF 3SO 3）（1）和[Cu-2（mtbz）（2）（CH 3 O）（2）]（ClO 4）（2）（4）进行了结构表征。1的晶体数据：单斜晶系，空间群P2（1）/c，a = 13.6585（5），B = 39.981（3），c = 20.919（1）埃，β = 125.98（1）度，Z = 8。4的晶体数据：单斜晶系，空间群P2（1）/c，a = 13.115（2），B = 9.523（2），c = 17.908（4）埃，β = 111.71（1）度，Z = 2。结构1和4各自由具有桥接甲氧基的双核单元和经由N原子连接到每个铜的一个配体组成。结构1（由两个双核，晶体学独立，但化学上相同的单元组成）具有由三氟甲磺酸根阴离子桥接的两个铜原子，为每个铜原子提供正方形金字塔配位，而结构4中的铜原子具有几乎正方形平面几何形状。双核单元内的Cu-Cu距离（埃）为：1，2.9775（13），2.9751（13）; 4，2.9872（16）; Cu-O-Cu桥连角（度）为：1，101.7（3），101.7（3），100.9（3），102.1（3）; 4，103.2（2）。中红外部分集中在三氟甲磺酸根阴离子的振动揭示了有趣的结果，有关的nu（as）（S-O）带的阴离子的分配。在远红外光谱中，发现甲氧基桥连化合物的特征Cu-O振动在386和230 cm（-1）处，乙氧基桥连化合物的特征Cu-O振动在454和332 cm（-1）处。这些双核物种是EPR沉默的，并且仅观察到单体杂质的弱信号。它们在室温以下也表现出抗磁性。
Based on the new ligand bis(1-methyl-2-benzimidazolyl) propane (abbreviated as mtbz) several new copper(II) coordination compounds have been prepared and characterized structurally and spectroscopically. Two representative compounds, i.e. [Cu-2(mtbz)(2)(CH3O)(2)(CF3SO3)](CF3SO3) (1) and [Cu-2(mtbz)(2)(CH3O)(2)](ClO4)(2) (4) were characterized structurally by X-ray diffraction. Crystal data for 1: monoclinic, space group P2(1)/c, a = 13.6585(5), b = 39.981(3), c = 20.919(1) Angstrom, beta = 125.98(1)degrees, Z = 8. Crystal data for 4: monoclinic, space group P2(1)/c, a = 13.115(2), b = 9.523(2), c = 17.908(4) Angstrom, beta = 111.71(1)degrees, Z = 2. Structures 1 and 4 each consist of a dinuclear unit with bridging methoxo groups and one ligand linked to each copper via an N atom. Structure 1 (which consists of two dinuclear, crystallographically independent, but chemically identical units) has the two copper atoms bridged by a triflate anion, providing each copper atom a square-pyramidal coordination, while the copper atoms in structure 4 have an almost a square-planar geometry. The Cu-Cu distances (Angstrom) within the dinuclear units are: 1, 2.9775(13), 2.9751(13); 4, 2.9872(16); the Cu-O-Cu bridging angles (degrees) are: 1, 101.7(3), 101.7(3), 100.9(3), 102.1(3); 4, 103.2(2). The mid-IR section focused on the vibrations of the triflate anion reveals interesting results concerning the assignment of that anion related to the nu(as)(S-O) band. Characteristic Cu-O vibrations in the far-IR section were found at 386 and 230 cm(-1) for the methoxo-bridged and 454 and 332 cm(-1) for the ethoxo-bridged compounds. These dinuclear species are EPR silent, and only a weak signal of monomeric impurities is observed. They also show a diamagnetic behavior below room temperature.