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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >The synthesis, structure and catalytic properties of the [Mo7O24(mu-Mo8O26)Mo7O24](16-) anion formed via two intermediate heptamolybdates [Co(en)(3)](2)[NaMo7O24]Cl center dot nH(2)O and (H3O)[Co(en)(3)](2)[Mo7O24]Cl center dot 9H(2)O
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The synthesis, structure and catalytic properties of the [Mo7O24(mu-Mo8O26)Mo7O24](16-) anion formed via two intermediate heptamolybdates [Co(en)(3)](2)[NaMo7O24]Cl center dot nH(2)O and (H3O)[Co(en)(3)](2)[Mo7O24]Cl center dot 9H(2)O

机译:通过两种中间庚酰胺酸盐形成的[MO7O24(MU-MO8O26)MO7O24](16-)阴离子的合成,结构和催化性能[CO(ZH)(3)](2)[Namo7O24] CL中心点NH(2) O和(H3O)[CO(EN)(3)](2)[MO7O24] CL中心点9H(2)O.

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摘要

Ageing a mixture of sodium molybdate, malonic acid, and tris(ethylenediamine) cobalt(III) chloride using different synthetic routes, namely, solution-based methods at room temperature or 110 degrees C, and a mechanochemically accelerated vapour-assisted method, yielded the polyoxomolybdate [Co(en)(3)](5)Na [Mo7O24(mu-Mo8O26)Mo7O24]center dot nH(2)O (1). The new polyoxomolybdate anion 1 comprised three fragments, namely, two {Mo7O24} units bridged by a {Mo8O26} unit, which were interconnected by the terminal oxygen atoms of MoO6 octahedra and represent a unique structural motif not yet described in the structurally versatile chemistry of polyoxomolybdates (POMos). The ageing reaction was found to occur via a series of intermediates, two of which were isolated and identified as the heptamolybdate coordination polymer [Co(en)(3)](2)[NaMo7O24]Cl center dot nH(2)O (2), comprising {Mo7O24} units bridged by a sodium atom, and the heptamolybdate (H3O)[Co(en)(3)](2)[Mo7O24]Cl center dot 9H(2)O (3). An identical reaction procedure with [Co(C2O4) (en)(2)](+) instead of [Co(en)(3)](3+) yielded the orthomolybdate [Co(C2O4)(en)(2)](2)[MoO4]center dot 9H(2)O (4) and the hydrogen malonate [Co(C2O4)(en)(2)]C3O4H3 (5). The new polyoxomolybdate [Co(en)(3)](5)Na [Mo7O24(mu-Mo8O26)Mo7O24]center dot nH(2)O was also examined as a catalyst for the epoxidation of cyclooctene, and was superior to both heptamolybdate and octamolybdate catalysts over 24 h. The heptamolybdate [Co(NH3)(6)](2)[Mo7O24]center dot 8H(2)O (6) was isolated as the only reaction product of sodium molybdate and hexaamminecobalt( III) nitrate in the presence of malonic acid using solution-based methods.
机译:使用不同的合成路线,老化钼酸钠,丙二酸,和三(乙二胺)钴(III)氯化物的混合物即,基于溶液的方法在室温或110℃,和一个机械化学加速蒸汽辅助的方法中,得到的polyoxomolybdate [CO(烯)(3)](5)的Na [Mo7O24(MU-Mo8O26)Mo7O24]中心点NH(2)O(1)。新polyoxomolybdate阴离子1包含三个片段,即,二{Mo7O24}单元桥接由{Mo8O26}单元,这是由MoO6八面体的末端氧原子相互连接,并且代表一种独特的结构基序尚未描述的结构通用性的化学polyoxomolybdates(POMos)。老化反应被发现通过一系列中间体,其中两个被分离并鉴定为七钼酸铵配位聚合物的产生[CO(烯)(3)](2)[NaMo7O24]氯中心点NH(2)O(2 ),包括{Mo7O24}单元桥接由钠原子,和七钼酸铵(H 3 O)[CO(烯)(3)](2)[Mo7O24]氯中心点9H(2)O(3)。用相同的反应程序[CO(C2O4)(烯)(2)](+)代替[CO(烯)(3)](3+)得到orthomolybdate [CO(C2O4)(烯)(2)] (2)[的MoO 4]中心点9H(2)O(4)和丙二酸氢[CO(C2O4)(烯)(2)] C3O4H3(5)。新polyoxomolybdate [CO(烯)(3)](5)的Na [Mo7O24(MU-Mo8O26)Mo7O24]中心点NH(2)O还检查了作为环辛烯环氧化的催化剂,并且优于两个七钼酸铵超过24小时,并八钼酸盐催化剂。 [Mo7O24]中心点8H(2)O(6)分离为钼酸钠和六氨基钴(Ⅲ)硝酸盐在丙二酸的存在的唯一反应产物使用七钼酸铵[CO(NH 3)(6)](2)基于溶液的方法。

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