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首页> 外文期刊>Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics >Ratio-Controlled Precursors of Anderson-Evans Polyoxometalates: Synthesis, Structural Transformation, and Magnetic and Catalytic Properties of a Series of Triol Ligand-Decorated {M2Mo6} Clusters (M = Cu2+, Co2+, Ni2+, Zn2+)
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Ratio-Controlled Precursors of Anderson-Evans Polyoxometalates: Synthesis, Structural Transformation, and Magnetic and Catalytic Properties of a Series of Triol Ligand-Decorated {M2Mo6} Clusters (M = Cu2+, Co2+, Ni2+, Zn2+)

机译：Anderson-emans的比例控制前体是一种多氧化物：一系列三醇配体装饰的{M2MO6}簇的合成，结构转化和磁性和催化性能（M = Cu2 +，CO 2 +，Ni2 +，Zn2 +）

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摘要

A series of triol ligand [CH3C(CH2OH)(3)] covalently decorated polyoxometalates (POMs), which could be ascribed to the primary complexes with structural formulas {M-2[Mo2O4(CH3C(CH2O)(3))(2)](3)}(2-) (M = Cu2+, Co2+, Ni2+, Zn2+), have been synthesized in organic solvents. Single-crystal X-ray structural analysis reveals that the synthesized polyanionic clusters are comprised of three {Mo-2} units and two divalent transition-metal ions connecting to each other in an alternating style, where all {Mo-2} blocks were covalently decorated by two triol ligands in the trans conformation. The 1/3 molar ratio of M/Mo in the prepared complexes was higher than those ratios in typical Anderson-Evans, Wells-Dawson, and Keggin POMs. With a decrease in the M/Mo molar ratio of a Mo-contained reactant to 1/6 and/or the addition of acetic acid to the reaction solution, the primary complexes acting as precursors transformed continuously into the corresponding triol-ligand-decorated Anderson-Evans POMs. Detailed investigations were conducted by using different isopolymolybdates in various solvent environments, and several Anderson-Evans POMs in different triol-ligand-decorated fashions were obtained from the primary complexes. In addition, we also realized the transformation between the Anderson-Evans clusters in different decoration fashions by simply controlling the acidity in solution. Magnetic measurement showed a general property, but the catalytic experiments demonstrated that Co-II- and Zn (II)-containing POMs displayed a higher efficiency for the selective oxidation of thioanisole to sulfoxide.
机译：一系列三醇配体[CH 3 C（CH 2 OH）（3）]共价装饰的多氧酸盐（POMS），其可与结构式甲状腺配合物归因于结构式（M-2 [MO2O4（CH 3 C（CH 2 O）（3））（2） （2-）（M = Cu 2 +，CO 2 +，Ni2 +，Zn2 +）已在有机溶剂中合成。单晶X射线结构分析表明，合成的多沉默簇由三个{Mo-2}单元和两个二价过渡 - 金属离子组成，并且在交替的样式中彼此连接，其中所有{mo-2}块共聚在反向构象中由两个三醇配体装饰。制备的配合物中的M / Mo的1/3摩尔比高于典型的安德森 - 埃文斯，井 - 道森和Keggin Poms中的比例。随着MO含有反应物的m / mo摩尔比的降低至1/6和/或向反应溶液中加入乙酸，作为前体的主要复合物连续转化为相应的三醇 - 配体装饰的安德森-evans poms。通过在各种溶剂环境中使用不同的异聚钼酸盐进行详细研究，并从初级复合物中获得不同三醇 - 配体装饰的时装中的几个Anderson-emans POM。此外，我们还通过简单地控制溶液中的酸度来实现不同装饰时尚的Anderson-evans集群之间的转变。磁性测量显示了一般性，但催化实验证明了CO-II-和Zn（II）的POMS显示出硫代烷对亚砜的选择性氧化较高的效率。

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