Cyclic polyvanadates incorporating template transition metal cationic species: synthesis and structures of hexavanadate [PdV6O18]4-, octavanadate [Cu2V8O24]4-, and decavanadate [Ni4V10O30(OH)2(H2O)6]4-.
Cyclic polyvanadates incorporating template transition metal cationic species: synthesis and structures of hexavanadate [PdV6O18]4-, octavanadate [Cu2V8O24]4-, and decavanadate [Ni4V10O30(OH)2(H2O)6]4-.
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DOI：
10.1021/ic048751f
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发表时间：
2005-03
影响因子：
4.6
通讯作者：
Taisei Kurata;A. Uehara;Y. Hayashi;K. Isobe
中科院分区：
文献类型：
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作者：
Taisei Kurata;A. Uehara;Y. Hayashi;K. Isobe
通过[VO 3]-阴离子与金属模板阳离子Pd（II）、Cu（II）和Ni（II）反应，合成了[（C2 H5）4 N] 4[PdV 6 O 18]（1）、[（C2 H5）4 N]4[Cu 2 V8 O24]（2）和[（C6 H5）4P]4[Ni 4V 10 O30（OH）2（H2O）6]（3）三种类型的杂多钒酸盐。1的X射线晶体结构（a = 29.952（4）A，B = 12.911（2）A，c = 13.678（2）A，正交晶系，空间群Pca 2（1），Z = 4），2（a = 13.740（1）A，B = 22.488（2）A，c = 18.505（2）A，β = 94.058（2）度，单斜晶系，空间群P2（1）/n，Z = 4），和3（a = 12.333（2）A，B = 16.208（4）A，c = 16.516（3）A，α = 112.438（3）度，β = 94.735（3）度，γ = 104.749（3）度，三斜晶系，空间群P，Z = 1）表明，金属阳离子物种诱导环状[VO 3]（n-）n（n = 6，8，10）环的形成，并且阳离子并入环本身中。在金属包合物中，环状钒酸盐作为大环配体，金属阳离子作为模板。环状钒酸盐由四面体VO 4单元组成，四面体VO 4单元共享角落并在分子中心掺入金属阳离子物质。碗状配合物1包括Pd 2+阳离子，其由船状六钒酸盐环的氧供体配位。抗磁性配合物1通过51 V和17 O NMR谱进行表征。配合物2包括一个八钒酸环和两个Cu 2+，它们位于由桥连钒原子的八个氧原子所定义的平均平面的两侧。在配合物3的情况下，具有封端的Ni 2+水离子的二-μ-羟基桥接的Ni 2+二聚体通过水解形成十钒酸盐环，其中两个四面体钒酸盐单元不与Ni 2+核心键合，而是通过封端的Ni 2+阳离子中的水配体由氢键支撑。使用ESI-MS研究，通过其特征同位素模式清楚地鉴定溶液中的络合物1-3。
Three types of heteropolyvanadates, [(C2H5)4N]4[PdV6O18] (1), [(C2H5)4N]4[Cu2V8O24] (2), and [(C6H5)4P]4[Ni4V10O30(OH)2(H2O)6] (3), were synthesized through the reaction between the [VO3]- anion and metal template cations of Pd(II), Cu(II), and Ni(II). The X-ray crystal structures of 1 (a = 29.952(4) A, b = 12.911(2) A, and c = 13.678(2) A, orthorhombic, space group Pca2(1) with Z = 4), 2 (a = 13.740(1) A, b = 22.488(2) A, c = 18.505(2) A, and beta= 94.058(2) degrees , monoclinic, space group P2(1)/n with Z = 4), and 3 (a = 12.333(2) A, b = 16.208(4) A, c = 16.516(3) A, alpha = 112.438(3) degrees , beta = 94.735(3) degrees , and gamma = 104.749(3) degrees , triclinic, space group P with Z = 1) demonstrate that the metal cationic species induced cyclic [VO3](n-)n (n = 6, 8, 10) ring formation and the cations are incorporated in the rings themselves. In the metal inclusion products, the cyclic vanadates act as macrocyclic ligands, in which the metal cationic species act as the templates. The cyclic vanadate is composed of tetrahedral VO4 units that share corners and incorporates a metal cationic species in the center of the molecules. The bowl-shaped complex 1 includes a Pd2+ cation that is coordinated by the oxygen donors of a boatlike hexavanadate ring. The diamagnetic complex 1 was characterized via 51V and 17O NMR spectroscopy. Complex 2 involves an octavanadate ring and two Cu2+, which are located on both sides of the mean plane as defined by the eight oxygen atoms that bridge the vanadium atoms. In the case of complex 3, the di-mu-hydroxo-bridged Ni2+ dimer with capped Ni2+ aqua ions is formed by hydrolysis to form the decavanadate ring, in which two of the tetrahedral vanadate units are not bonded to the Ni2+ core but supported by hydrogen bonds through the aqua-ligand in the capped Ni2+ cation. Complexes 1-3 in solution were clearly identified by their characteristic isotope patterns using ESI-MS studies.