非对称二核配体(μ-乙二酮)双(μ-烷氧基)二钴(II, III)配合物的合成与晶体结构

IF 0.1 Q4 CRYSTALLOGRAPHY
Naho Shinde, Ryunosuke Handa, H. Furutachi, Y. Sakata, Shigehisa Akine, S. Fujinami, Masatatsu Suzuki
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In this paper, we report on the crystal structure of a dicobalt(II, III) mixed-valence complex, [CoII Co(tpdb)(CH3CO2)(CH3O)](ClO4)2·0.75CH3OH· 0.25CH3CN (1) (Fig. 1), which was obtained by an oxidative degradation of [Co2(tpdb)(CH3CO2)] in methanol/acetonitrile at ambient temperature under air. A mixture of Co(ClO4)2·6H2O (0.366 g, 1.0 mmol) and Htpdb (0.235 g, 0.5 mmol) in methanol/acetonitrile (3:1, 12 mL) was added to a methanol solution (5 mL) containing CH3CO2Na·3H2O (0.07 g, 0.5 mmol) and triethylamine (69 μL, 0.5 mmol) to give a dark-brown solution. Oxygen gas was bubbled for 5 min into the solution. The resulting dark-brown solution was allowed to stand for several weeks at ambient temperature under air to give single crystals of [CoCo(tpdb)(CH3CO2)(CH3O)](ClO4)2· 0.75CH3OH· 0.25CH3CN (1) suitable for X-ray crystallography. Yield: 0.28 g, 63 % (Anal. Found: C, 41.20; H, 4.37; N, 9.28%. Calcd for [CoCo(tpdb)(CH3CO2)(CH3O)](ClO4)2·1.5H2O, C31H40Cl2Co2N6O13.5: C, 41.30; H, 4.47; N, 9.32%.). It was picked up from the solution by a loop on a hand-made cold copper plate mounted inside a liquid N2 Dewar vessel at –80°C; the loop was mounted on the diffractometer. 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)8 and expanded using a Fourier technique. The structure was refined by a full-matrix least-squares method by using SHELXL 20149 (Yadokari-XG).10 All non-hydrogen atoms were refined with anisotropic displacement parameters. The hydrogen atoms were included using a riding model. For the disordered anion and solvent molecules, occupancy factors were refined using distance/ADP restraints. The crystal data are summarized in Table 1. The X-ray crystallography of 1 reveals that the asymmetric unit contains a complex cation [CoCo(tpdb)(CH3CO2) (CH3O)], two ClO4, and 0.75 methanol and 0.25 acetonitrile molecule (Fig. S1). An ORTEP drawing of the complex cation, [CoCo(tpdb)(CH3CO2)(CH3O)] of 1, is shown in Fig. 2. Selected bond distances (Å) and angle (°) are given in Table 2. The complex cation of 1 has distinct cobalt centers that are triply bridged by alkoxo oxygens of tpdp and methoxo, and acetate group as found for closely related dicobalt(II, III) mixedvalence complex [CoCo(L)2(CH3CO2)(CH3O)2] (2) (L = N-methyl-N,N-bis(2-pyridylmethyl)amine).11 The Co1···Co2 separation is 2.9918 Å, which is slightly longer than that of 2 (2.956 Å). Both of the cobalt atoms in 1 have a distorted octahedral structure with an N3O3 donor set, where three 2021 © The Japan Society for Analytical Chemistry","PeriodicalId":23922,"journal":{"name":"X-ray Structure Analysis Online","volume":null,"pages":null},"PeriodicalIF":0.1000,"publicationDate":"2021-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Synthesis and Crystal Structure of (μ-Acetato)bis(μ-Alkoxo)dicobalt(II, III) Complex with an Unsymmetric Dinucleating Ligand\",\"authors\":\"Naho Shinde, Ryunosuke Handa, H. Furutachi, Y. Sakata, Shigehisa Akine, S. 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引用次数: 0

摘要

金属蛋白的双金属活性中心具有多种作用;使用简单双核金属配合物的模型研究对于深入了解这种双金属核心的生物学功能非常重要。1-5末端型双核配体,具有酚类和醇类氧作为内源性桥,已被用于模拟金属蛋白的羧酸桥接双金属活性位点。1-5之前,我们报道过氧配合物[Co2(tpdb)(O2)(CH3CO2)]和混合价配合物[FeFe(tpdb)(C6H5CO2)2]的合成和表征,它们具有不对称的吡啶基二核配体(tpdb)作为氰菊酯和紫色酸性磷酸酶的模型。本文报道了一种双钴(II, III)混价配合物[CoII Co(tpdb)(CH3CO2)(ch30)](ClO4)2·0.75CH3OH·0.25CH3CN(1)(图1)的晶体结构,该配合物是在空气环境下,由[Co2(tpdb)(CH3CO2)]在甲醇/乙腈中氧化降解得到的。将Co(ClO4)2·6H2O (0.366 g, 1.0 mmol)和Htpdb (0.235 g, 0.5 mmol)的甲醇/乙腈(3:1,12 mL)混合物加入到含有CH3CO2Na·3H2O (0.07 g, 0.5 mmol)和三乙胺(69 μL, 0.5 mmol)的甲醇溶液(5 mL)中,得到深棕色溶液。将氧气泡入溶液5分钟。得到的深棕色溶液在室温下空气下静置数周,得到适合x射线晶体学的[CoCo(tpdb)(CH3CO2)(ch30)](ClO4)2·0.75CH3OH·0.25CH3CN(1)单晶。收率:0.28 g, 63%。发现:C, 41.20;H, 4.37;N, 9.28%。[CoCo(tpdb)(CH3CO2)(ch30)](ClO4)2·1.5H2O, C31H40Cl2Co2N6O13.5: C, 41.30;H, 4.47;N, 9.32%)。在-80°C的温度下,通过安装在液态N2杜瓦容器内的手工制作的冷铜板上的环路从溶液中拾取;环路安装在衍射仪上。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)8求解,并采用傅里叶技术展开。采用SHELXL 20149 (Yadokari-XG)软件,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。对于无序阴离子和溶剂分子,使用距离/ADP约束来细化占用因子。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(tpdb)(CH3CO2) (ch30)],两个ClO4和0.75甲醇和0.25乙腈分子(图S1)。图2所示为1的络合阳离子[CoCo(tpdb)(CH3CO2)(ch30)]的ORTEP图。选择的键距(Å)和键角(°)如表2所示。1的配合物阳离子具有明显的钴中心,由tpdp和methoxo的烷氧氧三桥接,并且在密切相关的二钴(II, III)混合价配合物[CoCo(L)2(CH3CO2)(ch30)2] (2) (L = n -甲基- n, n -二(2-吡啶基甲基)胺)中发现了乙酸基Co1···Co2的分离时间为2.9918 Å,略长于2的分离时间(2.956 Å)。1中的两个钴原子都具有扭曲的八面体结构,具有N3O3供体集,其中三个2021©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。
Synthesis and Crystal Structure of (μ-Acetato)bis(μ-Alkoxo)dicobalt(II, III) Complex with an Unsymmetric Dinucleating Ligand
The bimetallic active centers of metalloproteins exhibit versatile roles; model studies using simple dinuclear metal complexes are important in order to gain insight into the biological functions of such bimetallic cores.1–5 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.1–5 Previously, we reported on the synthesis and characterization of a peroxo complex, [Co2(tpdb)(O2)(CH3CO2)], and a mixed-valence complex, [FeFe(tpdb)(C6H5CO2)2], having an unsymmetric dinucleating ligand with pyridyl groups (tpdb) as models for hemerythrin and purple acid phosphatase. In this paper, we report on the crystal structure of a dicobalt(II, III) mixed-valence complex, [CoII Co(tpdb)(CH3CO2)(CH3O)](ClO4)2·0.75CH3OH· 0.25CH3CN (1) (Fig. 1), which was obtained by an oxidative degradation of [Co2(tpdb)(CH3CO2)] in methanol/acetonitrile at ambient temperature under air. A mixture of Co(ClO4)2·6H2O (0.366 g, 1.0 mmol) and Htpdb (0.235 g, 0.5 mmol) in methanol/acetonitrile (3:1, 12 mL) was added to a methanol solution (5 mL) containing CH3CO2Na·3H2O (0.07 g, 0.5 mmol) and triethylamine (69 μL, 0.5 mmol) to give a dark-brown solution. Oxygen gas was bubbled for 5 min into the solution. The resulting dark-brown solution was allowed to stand for several weeks at ambient temperature under air to give single crystals of [CoCo(tpdb)(CH3CO2)(CH3O)](ClO4)2· 0.75CH3OH· 0.25CH3CN (1) suitable for X-ray crystallography. Yield: 0.28 g, 63 % (Anal. Found: C, 41.20; H, 4.37; N, 9.28%. Calcd for [CoCo(tpdb)(CH3CO2)(CH3O)](ClO4)2·1.5H2O, C31H40Cl2Co2N6O13.5: C, 41.30; H, 4.47; N, 9.32%.). It was picked up from the solution by a loop on a hand-made cold copper plate mounted inside a liquid N2 Dewar vessel at –80°C; the loop was mounted on the diffractometer. 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)8 and expanded using a Fourier technique. The structure was refined by a full-matrix least-squares method by using SHELXL 20149 (Yadokari-XG).10 All non-hydrogen atoms were refined with anisotropic displacement parameters. The hydrogen atoms were included using a riding model. For the disordered anion and solvent molecules, occupancy factors were refined using distance/ADP restraints. The crystal data are summarized in Table 1. The X-ray crystallography of 1 reveals that the asymmetric unit contains a complex cation [CoCo(tpdb)(CH3CO2) (CH3O)], two ClO4, and 0.75 methanol and 0.25 acetonitrile molecule (Fig. S1). An ORTEP drawing of the complex cation, [CoCo(tpdb)(CH3CO2)(CH3O)] of 1, is shown in Fig. 2. Selected bond distances (Å) and angle (°) are given in Table 2. The complex cation of 1 has distinct cobalt centers that are triply bridged by alkoxo oxygens of tpdp and methoxo, and acetate group as found for closely related dicobalt(II, III) mixedvalence complex [CoCo(L)2(CH3CO2)(CH3O)2] (2) (L = N-methyl-N,N-bis(2-pyridylmethyl)amine).11 The Co1···Co2 separation is 2.9918 Å, which is slightly longer than that of 2 (2.956 Å). Both of the cobalt atoms in 1 have a distorted octahedral structure with an N3O3 donor set, where three 2021 © The Japan Society for Analytical Chemistry
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CiteScore
0.60
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50.00%
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