The synthesis, structure and catalytic properties of the [Mo<sub>7</sub>O<sub>24</sub>(μ-Mo<sub>8</sub>O<sub>26</sub>)Mo<sub>7</sub>O<sub>24</sub>]<sup>16−</sup> anion formed <i>via</i> two intermediate heptamolybdates [Co(en)<sub>3</sub>]<sub>2</sub>[NaMo<sub>7</sub>O<sub>24</sub>]Cl·<i>n</i>H<sub>2</sub>O and (H<sub>3</sub>O)[Co(en)<sub>3</sub>]<sub>2</sub>[Mo<sub>7</sub>O<sub>24</sub>]Cl·9H<sub>2</sub>O
coordination polymer [Co(en)3]2[NaMo7O24]Cl·nH2O (2), comprising Mo7O24} units bridged by a sodium atom, and the heptamolybdate (H3O)[Co(en)3]2[Mo7O24]Cl·9H2O (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]·9H2O (4) and the hydrogen malonate [Co(C2O4)(en)2]C3O4H3 (5). The new polyoxomolybdate [Co(en)3]5Na[Mo7O24(μ-Mo8O26)Mo7O24]·nH2O
使用不同的合成途径(即,在室温或110°C下基于溶液的方法以及机械化学加速的蒸气辅助方法)使钼酸钠,丙二酸和三(乙二胺)氯化钴(III)的混合物老化,从而产生了polyoxomolybdate [CO(烯)3 ] 5的Na [沫7 ø 24(μ-沫8 ö 26)的Mo 7 ø 24 ]· ñ ħ 2 O(1)。新的聚氧钼酸根阴离子1包含三个片段,即由Mo 8桥接的两个Mo 7 O 24 }单元O 26 }单元通过MoO 6八面体的末端氧原子相互连接,代表了在聚氧钼酸酯(POMos)的结构通用化学中尚未描述的独特结构基序。发现老化反应是通过一系列中间体发生的,其中两种中间体被分离并鉴定为七钼酸配位聚合物[Co(en)3 ] 2 [NaMo 7 O 24 ] Cl· n H 2 O(2),包括由钠原子与七钼酸盐(H 3 O)[Co(en)3桥接的Mo 7 O 24 }单元] 2 [Mo 7
Supramolecular assembly of oxalatomolybdates controlled by the hydrogen bonding potential of Co(<scp>iii</scp>)-ammine cations
possibility of controlling the formation of oxalatomolybdate anions by the choice of a counterion and adjustment of pH was presented. Using four CoIII(ammine) macrocations ([Co(NH3)6]3+, [Co(NO2)(NH3)5]2+, [Co(en)3]3+ and [Co(ox)(en)2]+) in acidic aqueous solutions, ten crystalline solids were obtained. They were found to contain a total of six different oxalatomolybdate species, three of which, a
提出了通过选择抗衡离子和调节pH值来控制草酰钼酸盐阴离子形成的可能性的系统研究。使用四个Co III(氨基)大阳离子([Co(NH 3)6 ] 3+,[Co(NO 2)(NH 3)5 ] 2 +,[Co(en)3 ] 3+和[Co(ox) (en)2 ] +)在酸性水溶液中,获得十种结晶固体。发现它们总共包含六种不同的草酰钼酸盐,其中三种是环状四聚体[Mo 2 O 4(μ-O)2(ox)2 ] 2 8−,线性四聚体[Mo 4 O 8(μ-O)3(ox)4(H 2 O)2 ] 6−和聚合物[Mo 4 O 11(ox)4( H 2 O)] n 6 n –迄今尚未报告。在固体中发现的草酰草酸盐种类确实与溶液中的主要种类相对应,该溶液是从中获得它们的溶液的pH值。这些物质的缩合可能与所用的大阳离子(Co(III)。
The Stereochemistry of Complex Inorganic Compounds. I. The Walden Inversion as Exhibited by Diethylenediaminocobaltic Compounds