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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+)
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2018-03-19 00:00:00 , DOI: 10.1021/acs.inorgchem.7b02996 Yang Wang 1 , Xueping Kong , Wei Xu , Fengrui Jiang , Bao Li , Lixin Wu
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2018-03-19 00:00:00 , DOI: 10.1021/acs.inorgchem.7b02996 Yang Wang 1 , Xueping Kong , Wei Xu , Fengrui Jiang , Bao Li , Lixin Wu
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A series of triol ligand [CH3C(CH2OH)3] covalently decorated polyoxometalates (POMs), which could be ascribed to the primary complexes with structural formulas {M2[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 {Mo2} units and two divalent transition-metal ions connecting to each other in an alternating style, where all {Mo2} 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 CoII- and Zn II-containing POMs displayed a higher efficiency for the selective oxidation of thioanisole to sulfoxide.
中文翻译：
比例控制的Anderson-Evans多金属氧酸盐的前体：一系列三醇配体修饰的{M 2 Mo 6 }团簇（M = Cu 2 +，Co 2 +，Ni 2+，锌2+）
一系列三醇配体[CH 3 C（CH 2 OH）3 ]共价修饰的多金属氧酸盐（POM），可以归结为具有结构式{M 2 [Mo 2 O 4（CH 3 C（CH 2 O ）3）2 ] 3 } 2–（M = Cu 2 +，Co 2 +，Ni 2 +，Zn 2+）已经在有机溶剂中合成。X射线单晶结构分析表明，合成的聚阴离子团簇由三个{Mo 2}单元和两个二价过渡金属离子以交替方式相互连接，其中所有{Mo 2}嵌段由反式构象中的两个三醇配体共价修饰。制备的配合物中M / Mo的1/3摩尔比高于典型的Anderson–Evans，Wells–Dawson和Keggin POM中的摩尔比。随着含Mo的反应物的M / Mo摩尔比与1/6的降低和/或向反应溶液中添加乙酸的作用，作为前体的主要络合物连续转化为相应的三醇配体修饰的Anderson –Evans POM。在不同的溶剂环境中使用不同的异多钼酸盐进行了详细的研究，并从主要配合物中获得了几种具有不同三醇配体修饰方式的Anderson-Evans POM。此外，通过简单地控制溶液中的酸度，我们还实现了以不同装饰方式实现的安德森-埃文斯簇之间的转换。磁测量显示出一般性质，但催化实验表明，Co含II-和Zn II的POM对硫代苯甲醚选择性氧化为亚砜显示出更高的效率。
更新日期：2018-03-19
中文翻译：
比例控制的Anderson-Evans多金属氧酸盐的前体：一系列三醇配体修饰的{M 2 Mo 6 }团簇（M = Cu 2 +，Co 2 +，Ni 2+，锌2+）
一系列三醇配体[CH 3 C（CH 2 OH）3 ]共价修饰的多金属氧酸盐（POM），可以归结为具有结构式{M 2 [Mo 2 O 4（CH 3 C（CH 2 O ）3）2 ] 3 } 2–（M = Cu 2 +，Co 2 +，Ni 2 +，Zn 2+）已经在有机溶剂中合成。X射线单晶结构分析表明，合成的聚阴离子团簇由三个{Mo 2}单元和两个二价过渡金属离子以交替方式相互连接，其中所有{Mo 2}嵌段由反式构象中的两个三醇配体共价修饰。制备的配合物中M / Mo的1/3摩尔比高于典型的Anderson–Evans，Wells–Dawson和Keggin POM中的摩尔比。随着含Mo的反应物的M / Mo摩尔比与1/6的降低和/或向反应溶液中添加乙酸的作用，作为前体的主要络合物连续转化为相应的三醇配体修饰的Anderson –Evans POM。在不同的溶剂环境中使用不同的异多钼酸盐进行了详细的研究，并从主要配合物中获得了几种具有不同三醇配体修饰方式的Anderson-Evans POM。此外，通过简单地控制溶液中的酸度，我们还实现了以不同装饰方式实现的安德森-埃文斯簇之间的转换。磁测量显示出一般性质，但催化实验表明，Co含II-和Zn II的POM对硫代苯甲醚选择性氧化为亚砜显示出更高的效率。
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