Unique tetranuclear copper(II) cluster and monomeric iron(II), (III) complexes with a tris(imidazolyl) chelating ligand

Liang Ping Wu; Yoshiro Yamagiwa; Ichirou Ino; Kunihisa Sugimoto; Takayoshi Kuroda-Sowa; Tadao Kamikawa; Megumu Munakata

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Unique tetranuclear copper(II) cluster and monomeric iron(II), (III) complexes with a tris(imidazolyl) chelating ligand

机译：独特的四核铜（II）簇和具有三（咪唑基）螯合配体的单体铁（II）（III）配合物

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Copper(II) and iron(II, III) complexes of the tripodal ligand, tris(1-methyl-1H-imidazol-2-yl)methanol (Htmim), have been synthesized and characterized by elemental analysis, ~1H NMR and IR spectroscopies, magnetic moment measurement and X-ray crystallography. The structure of the copper complex, [Cu_4(tmim)_4(CF_3SO_3)_2](CF_3SO_3)_2 centre dot 2MeOH (1), can be regarded as a polyimidazole-linked tetranuclear cluster where each copper atom adopts a five-coordinate square-pyramidal geometry ligated by the tmim anion. The two iron complexes, [Fe~(II)(Htmim)_2][Fe~(II)Cl_4] center dot 4MeOH (2) and [Fe~(III)(Htmim)_2][Fe~(III)Cl_4]_2Cl (3), contain the isostructural [Fe(Htmin)_2] cation and tetrahedral [FeCl_4]~- anion. While Htmim shows a normal tripodal tridentate mode in the iron complexes capping one face of an essentially octahedral coordination sphere, its deprotonated species exhibit an unusual non-tripodal tetradentate coordination with copper(II) ions. The observed magnetic moment at room temperature for 1 is 1.13 BM per Cu atom, consistent with antiferromagnetic coupling between the copper(II) atoms of the tetramer. Both 2 and 3 show magnetic properties consistent with low-spin electronic configurations of the cation and high-spin nature of the metal ion in the anion.

机译：已合成三脚架配体的三（1-甲基-1H-咪唑-2-基）甲醇（Htmim）的铜（II）和铁（II，III）配合物，并通过元素分析，〜1H NMR和IR进行了表征光谱学，磁矩测量和X射线晶体学。铜络合物[Cu_4（tmim）_4（CF_3SO_3）_2]（CF_3SO_3）_2中心点2MeOH（1）的结构可以看作是聚咪唑连接的四核簇，其中每个铜原子均采用五坐标正方形的- tmim阴离子束缚了金字塔形几何形状。两种铁配合物[Fe〜（II）（Htmim）_2] [Fe〜（II）Cl_4]中心点4MeOH（2）和[Fe〜（III）（Htmim）_2] [Fe〜（III）Cl_4] _2Cl（3）含有同构结构的[Fe（Htmin）_2]阳离子和四面体[FeCl_4]〜-阴离子。虽然Htmim在覆盖基本为八面体配位球的一面的铁络合物中显示出正常的三脚架三齿模式，但其去质子化的物种表现出与铜（II）离子不同寻常的非三脚架四齿配位。在室温下观察到的每1个铜原子的磁矩为1.13 BM，这与四聚体的铜（II）原子之间的反铁磁耦合相符。 2和3都显示出与阳离子的低旋电子构型和阴离子中的金属离子的高旋性质一致的磁性能。

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来源
《Polyhedron: The International Journal for Inorganic and Organometallic Chemistry》 |1999年第15期|共7页
作者
Liang Ping Wu; Yoshiro Yamagiwa; Ichirou Ino; Kunihisa Sugimoto; Takayoshi Kuroda-Sowa; Tadao Kamikawa; Megumu Munakata;
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正文语种 eng
中图分类化学;无机化学;
关键词
crystal structures; copper(II) complex; tetranuclear cluster; iron complexes; imidazole; tris(imidazolyl) ligand;

机译：晶体结构;铜（II）配合物;四核簇;铁配合物;咪唑;三（咪唑基）配体;

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1. Unique tetranuclear copper(II) cluster and monomeric iron(II), (III) complexes with a tris(imidazolyl) chelating ligand [J] . Liang Ping Wu, Yoshiro Yamagiwa, Ichirou Ino, Polyhedron: The International Journal for Inorganic and Organometallic Chemistry . 1999,第15期

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2. Siderophore analogues: a new macrocyclic tetraamine tris (hydroxamate) ligand; synthesis and solution chemistry of the iron (III), aluminium (III) and copper (II) complexes [J] . Margarida Gaspar, Raquel Grazina, Andrea Bodor, Journal of the Chemical Society, Dalton Transactions. Inorganic Chemistry . 1999,第5期

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4. Synthesis of a tetranuclear vanadium cubane-type cluster protected by Co(III) complexes with 1,4,7-triazacyclononane ligands [C] . Keisuke Kawamoto, Sugiarto, Yoshihito Hayashi 日本化学会春季年会講演予稿集 . 2018

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5. Carboxamido nitrogen: A versatile new donor group which imparts unique properties to iron(III) and copper(II) complexes. [D] . Marlin, Dana Stewart. 2001

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Unique tetranuclear copper(II) cluster and monomeric iron(II), (III) complexes with a tris(imidazolyl) chelating ligand

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