二核配体(μ-苯氧基)双(μ-五氟苯甲酸酯)二钴(II, III)配合物的晶体结构

IF 0.1 Q4 CRYSTALLOGRAPHY
Naho Shinde, H. Furutachi, Y. Sakata, Shigehisa Akine, S. Fujinami, Masatatsu Suzuki
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A mixture of Co(ClO4)2·6H2O (0.183 g, 0.5 mmol) and Hbpmp (0.133 g, 0.25 mmol) in methanol (20 mL) was added a methanol solution (5 mL) containing C6F5CO2H (0.106 g, 0.5 mmol) and triethylamine (69 μL, 0.5 mmol) to give a darkbrown solution under air. Diethyl ether (30 mL) was added to the resulting dark-brown solution to give a black powder, which was recrystallized from acetonitrile/diethyl ether to give single crystals of [CoCo(bpmp)(C6F5CO2)2](ClO4)2·C2H5OC2H5 (1) suitable for X-ray crystallography. Yield: 0.09 g, 27% (Anal. Found: C, 44.49; H, 3.37; N, 7.68%. Calcd for [CoIICoIII(bpmp)(C6F5CO2)2](ClO4)2·1.5CH3CN·1.5H2O, C50H40.5Cl2Co2F10N7.5O14.5: C, 44.25; H, 3.01; N, 7.74%.). It was picked up on a hand-made cold copper plate mounted inside a liquid N2 Dewar vessel and mounted on a glass rod at –80°C. X-ray diffraction measurements were made on a Bruker D8 VENTURE diffractometer (Cu Kα radiation) at 90 K. 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The complex cation of 1 has distinct cobalt centers that are triply bridged by phenoxide oxygen of bpmp, and two pentafluorobenzoate groups as found for closely related dimetal(II, III) mixed valence complexes, [FeIIFeIII(bpmp)(C2H5CO2)2] (2)12 and [MnMn(bpmp)(C6H5CO2)2] (3).8 2020 © The Japan Society for Analytical Chemistry","PeriodicalId":23922,"journal":{"name":"X-ray Structure Analysis Online","volume":null,"pages":null},"PeriodicalIF":0.1000,"publicationDate":"2020-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"1","resultStr":"{\"title\":\"Crystal Structure of (μ-Phenoxo)bis(μ-pentafluorobenzoate)dicobalt(II, III) Complex with a Dinucleating Ligand\",\"authors\":\"Naho Shinde, H. Furutachi, Y. Sakata, Shigehisa Akine, S. 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A mixture of Co(ClO4)2·6H2O (0.183 g, 0.5 mmol) and Hbpmp (0.133 g, 0.25 mmol) in methanol (20 mL) was added a methanol solution (5 mL) containing C6F5CO2H (0.106 g, 0.5 mmol) and triethylamine (69 μL, 0.5 mmol) to give a darkbrown solution under air. Diethyl ether (30 mL) was added to the resulting dark-brown solution to give a black powder, which was recrystallized from acetonitrile/diethyl ether to give single crystals of [CoCo(bpmp)(C6F5CO2)2](ClO4)2·C2H5OC2H5 (1) suitable for X-ray crystallography. Yield: 0.09 g, 27% (Anal. Found: C, 44.49; H, 3.37; N, 7.68%. Calcd for [CoIICoIII(bpmp)(C6F5CO2)2](ClO4)2·1.5CH3CN·1.5H2O, C50H40.5Cl2Co2F10N7.5O14.5: C, 44.25; H, 3.01; N, 7.74%.). It was picked up on a hand-made cold copper plate mounted inside a liquid N2 Dewar vessel and mounted on a glass rod at –80°C. X-ray diffraction measurements were made on a Bruker D8 VENTURE diffractometer (Cu Kα radiation) at 90 K. 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引用次数: 1

摘要

末端型双核配体以酚氧和醇氧为内源性桥接,已被用于模拟金属蛋白的羧酸桥接双金属活性位点1-4,如甲氰菊酯(Hr)5和甲烷单加氧酶(MMO) 6已知金属蛋白的双金属活性中心具有不同的氧化态:二金属(II, II)、二金属(II, III)、二金属(III, III)、二金属(III, III)、二金属(III, IV)和二金属(IV, IV)。1 - 6具有不同氧化态的合成模型配合物对于获得金属蛋白活性中心的结构和光谱性质的基本见解特别重要。1-4之前,我们报道了混合价配合物[FeFe(bpmp)(RCO2)2]和[MnMn(bpmp)(RCO2)2] (R = CH3和C6H5)的合成和表征,它们具有末端型吡啶基二核配体(bpmp)。在本文中,我们报道了二钴(II, III)混合价配合物[CoCo(bpmp)(C6F5CO2)2](ClO4)2·C2H5OC2H5(1)的晶体结构(图1)。将Co(ClO4)2·6H2O (0.183 g, 0.5 mmol)和Hbpmp (0.133 g, 0.25 mmol)在甲醇(20 mL)中的混合物加入含有C6F5CO2H (0.106 g, 0.5 mmol)和三乙胺(69 μL, 0.5 mmol)的甲醇溶液(5 mL)中,得到空气下的深棕色溶液。在得到的深棕色溶液中加入乙醚(30ml)得到黑色粉末,由乙腈/乙醚重结晶得到适合x射线结晶学的[CoCo(bpmp)(C6F5CO2)2](ClO4)2·C2H5OC2H5(1)单晶。收率:0.09 g, 27%。发现:C, 44.49;H, 3.37;N, 7.68%。[CoIICoIII(bpmp)(C6F5CO2)2](ClO4)2·1.5CH3CN·1.5H2O, C50H40.5Cl2Co2F10N7.5O14.5: C, 44.25;H, 3.01;N, 7.74%)。在-80°C的温度下,将其置于液态氮气杜瓦容器内的手工制作的冷铜板上,并安装在玻璃棒上。用Bruker D8 VENTURE衍射仪(Cu Kα辐射)在90k下进行了x射线衍射测量。该结构采用直接法(SHELXT)9求解,并采用傅里叶技术展开。采用SHELXL 201410 (Yadokari-XG),采用全矩阵最小二乘法对结构进行优化所有非氢原子均采用各向异性位移参数进行细化。氢原子是用骑乘模型计算出来的。晶体数据汇总于表1。1的x射线晶体学显示,不对称单元包含一个配合阳离子[CoCo(bpmp)(C6F5CO2)2],两个ClO4和一个乙醚分子,其中一个ClO4在两个方向上无序。图2为1的络合阳离子[CoCo(bpmp)(C6F5CO2)2]的ORTEP图。所选键距(Å)和键角(°)见表2。1的配合物阳离子具有明显的钴中心,由bpmp的苯氧氧三桥接,并在密切相关的二金属(II, III)混合价配合物中发现两个五氟苯甲酸基团,[FeIIFeIII(bpmp)(C2H5CO2)2](2)12和[MnMn(bpmp)(C6H5CO2)2](3)。8 2020©日本分析化学学会
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Crystal Structure of (μ-Phenoxo)bis(μ-pentafluorobenzoate)dicobalt(II, III) Complex with a Dinucleating Ligand
The end-off type dinucleating ligands, having a phenolic and alcoholic oxygen as an endogenous bridge, have been used for modeling carboxylate-bridged bimetallic active sites of metalloproteins,1–4 such as hemerythrin (Hr)5 and methane monooxygenase (MMO).6 The bimetallic active centers of metalloproteins have been known to exhibit various oxidation states: dimetal(II, II), dimetal(II, III), dimetal(III, III), dimetal (III, IV), and dimetal(IV, IV).1–6 Synthetic model complexes with various oxidation states are of particular importance for obtaining fundamental insights into structural and spectroscopic properties of the active centers in metalloproteins.1–4 Previously, we reported on the synthesis and characterization of mixed-valence complexes, [FeFe(bpmp)(RCO2)2] and [MnMn(bpmp)(RCO2)2] (R = CH3 and C6H5), having an end-off type dinucleating ligand with pyridyl groups (bpmp).7,8 In this paper, we report on the crystal structure of the dicobalt(II, III) mixed-valence complex [CoCo(bpmp)(C6F5CO2)2](ClO4)2·C2H5OC2H5 (1) (Fig. 1). A mixture of Co(ClO4)2·6H2O (0.183 g, 0.5 mmol) and Hbpmp (0.133 g, 0.25 mmol) in methanol (20 mL) was added a methanol solution (5 mL) containing C6F5CO2H (0.106 g, 0.5 mmol) and triethylamine (69 μL, 0.5 mmol) to give a darkbrown solution under air. Diethyl ether (30 mL) was added to the resulting dark-brown solution to give a black powder, which was recrystallized from acetonitrile/diethyl ether to give single crystals of [CoCo(bpmp)(C6F5CO2)2](ClO4)2·C2H5OC2H5 (1) suitable for X-ray crystallography. Yield: 0.09 g, 27% (Anal. Found: C, 44.49; H, 3.37; N, 7.68%. Calcd for [CoIICoIII(bpmp)(C6F5CO2)2](ClO4)2·1.5CH3CN·1.5H2O, C50H40.5Cl2Co2F10N7.5O14.5: C, 44.25; H, 3.01; N, 7.74%.). It was picked up on a hand-made cold copper plate mounted inside a liquid N2 Dewar vessel and mounted on a glass rod at –80°C. X-ray diffraction measurements were made on a Bruker D8 VENTURE diffractometer (Cu Kα radiation) at 90 K. The structure was solved by a direct method (SHELXT)9 and expanded using a Fourier technique. The structure was refined by a full-matrix least-squares method by using SHELXL 201410 (Yadokari-XG).11 All non-hydrogen atoms were refined with anisotropic displacement parameters. The hydrogen atoms were included using a riding model. The crystal data are summarized in Table 1. The X-ray crystallography of 1 reveals that the asymmetric unit contains a complex cation [CoCo(bpmp)(C6F5CO2)2], two ClO4, and a diethyl ether molecule, where one of ClO4 is disordered over two orientations. An ORTEP drawing of the complex cation, [CoCo(bpmp)(C6F5CO2)2] of 1, is shown in Fig. 2. Selected bond distances (Å) and angles (°) are given in Table 2. The complex cation of 1 has distinct cobalt centers that are triply bridged by phenoxide oxygen of bpmp, and two pentafluorobenzoate groups as found for closely related dimetal(II, III) mixed valence complexes, [FeIIFeIII(bpmp)(C2H5CO2)2] (2)12 and [MnMn(bpmp)(C6H5CO2)2] (3).8 2020 © The Japan Society for Analytical Chemistry
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