• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>Chemistry: A European journal >Self-Condensation of [Mo~v_2O_2S_2]~2+ with Phosphate or Arsenate Ions by Acid - Base Processes in Aqueous Solution: Syntheses, Crystal Structures, and eactivity of [(HXO_4)_4Mo_6S_6O_6(OH)_3]~5-, X = P, As
【24h】

Self-Condensation of [Mo~v_2O_2S_2]~2+ with Phosphate or Arsenate Ions by Acid - Base Processes in Aqueous Solution: Syntheses, Crystal Structures, and eactivity of [(HXO_4)_4Mo_6S_6O_6(OH)_3]~5-, X = P, As

机译：[Mo〜v_2O_2S_2]〜2 +与磷酸盐或砷酸根在水溶液中的酸碱过程自缩合：[（HXO_4）_4Mo_6S_6O_6（OH）_3]〜5-的合成，晶体结构和活度，X = P，砷

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

The self-condensation of dithiocations [Mo_2S_2O_2]~2+ in aqueous solution in the presence of arsenate or phosphate ions as assembling groups led at pH 4-5 to hexanuclear [H_7X_4Mo_6S_6O+_25]~5- heteropolyoxothio anions 1 (X = P) and 2 (X = As). Both 1 and 2 were isolated in teh solid state in good yield as mixed cesium - sodium salts and were characterized unambiguosly by elemental analysis, IR and ~31P NMR spectroscopy, and single-crystal X-ray structuralk analysis. Rb_4Na_1.75Cl_0.75[H_7P_4Mo_6S_6O_25].8H_2O (b) crystallizes in the rhombohedral space group R3 (a = 13.352(3), b = 13.352(3), c = 39.708(10) A) and Rb_3.5Na_1.5[H_7As_4Mo_6S_6O_25].11H_2O (2b) in the triclinic P1 space group (a = 12.967(1), b = 13.271(1), c = 15.870(1) A, #alpha# = 101.11(1)deg, #beta# = 91.81(1)deg, #gamma# = 115.94(1)deg). The anions in 1b and 2b exhibit similar molecular structures, which consist of three {Mo_2O_2S_2] units surrounding a single central XO_4 group and mutually connected by three hydroxo bridges and three peripheral phosphate or arsenate groups. There is an interesting possibility of substituting the peripheral XO_4 groups. A variable-temperature ~31P NMR study of 1 in solution revealed a dynamci exchange between peripheral phosphate groups and uncoordinated phosphate ions. ~31P NMR also gave evidence of the successive replacemetn of arsenate by phosphate groups in 2. The apparent exchange ocnstants that were calculated were in agreement with a nearly pure statistical exchange between arsenate and phosphate groups. The substitution of the phosphate by acetate ligands in 1 was also examined. ~31P NMR spectra agreed with the successive formation of the mono-, di- and triacetato complexes. The very god agreemetn between teh calclated and experimetnal distribution of substituted compouds confirmed the ~31P NMR assignments and the proposed exchange scheme.
机译：在砷酸根或磷酸根离子为组装基团的情况下，水溶液中二硫代阳离子[Mo_2S_2O_2]〜2 +的自缩合导致pH 4-5生成六核[H_7X_4Mo_6S_6O + _25]〜5-杂多氧代硫代阴离子1（X = P）和2（X = As）。 1和2都以混合的铯-钠盐形式以高产率分离出，并通过元素分析，IR和〜31P NMR光谱以及单晶X射线结构分析明确表征。 Rb_4Na_1.75Cl_0.75 [H_7P_4Mo_6S_6O_25] .8H_2O（b）在菱面体空间群R3（a = 13.352（3），b = 13.352（3），c = 39.708（10）A）和Rb_3.5Na_1.5 [三斜P1空间组中的H_7As_4Mo_6S_6O_25] .11H_2O（2b）（a = 12.967（1），b = 13.271（1），c = 15.870（1）A，＃alpha＃= 101.11（1）deg，＃beta＃= 91.81（1）deg，＃gamma＃= 115.94（1）deg）。 1b和2b中的阴离子表现出相似的分子结构，由围绕单个中心XO_4基团并通过三个羟基桥和三个外围磷酸根或砷酸根相互连接的三个{Mo_2O_2S_2]单元组成。替换外围XO_4组有一种有趣的可能性。溶液中1的可变温度〜31P NMR研究表明，外围磷酸盐基团与未配位的磷酸盐离子之间发生了动态交换。约31 P NMR还提供了2中磷酸根连续取代砷酸根的证据。计算得出的表观交换指数与砷酸根与磷酸根基团之间几乎纯的统计交换相符。还检查了乙酸盐配体1中磷酸盐的取代。 〜31P NMR光谱与单，双和三乙酰基络合物的连续形成相符。取代化合物的计算值和实验值分布之间非常一致，证实了〜31P NMR分配和拟议的交换方案。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号