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硝酸钍氧化膦取代杯芳烃配合物的合成与结构

Synthesis and Crystal Structure of a Thorium(Ⅳ) Nitrate Complex with Phosphinoxide[-CH2P(O)Ph2]-substituted Calix[4]arene

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【作者】 赵明新朱文祥马淑兰袁大强王哲明

【Author】 ZHAO, Ming-Xin a ZHU, Wen-Xiang ,a MA, Shu-Lan a YUAN, Da-Qiang a WANG, Zhe-Ming b ( a Department of Chemistry, Beijing Normal University, Beijing 100875) ( b State Key Laboratory of Rare Earth Materials Chemistry and Application, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871)

【机构】 北京师范大学化学系北京大学化学与分子工程学院稀土材料化学与应用国家实验室 北京100875北京100875北京100871

【摘要】 合成了一种硝酸钍与氧化膦取代杯芳烃衍生物的配合物 ,[L·Th(OH2 ) (NO3 ) 2 ] [Th(NO3 ) 6]·CH3 CN {L =四 (亚甲基二苯基氧化膦 )杯 [4 ]芳烃 }.通过元素分析和红外光谱对配合物进行了表征 .用X射线单晶衍射法测定了其晶体结构 .晶体属三斜晶系 ,P 1空间群 ,晶胞参数a =1 990 ( 7)nm ,b =2 2 17( 8)nm ,c =2 890 ( 10 )nm ;α =10 4 92 ( 12 )° ,β =10 0 76( 14 )° ,γ =93 13 ( 10 )° ,Z =4;V =12 0 3 3 ( 7)nm3 ,R1=0 0 90 1,wR2 =0 190 7.此配合物由配阳离子和配阴离子构成 .配阳离子中 ,1个Th4+ 与杯芳烃中的 4个磷氧键上的氧原子 ,2个双齿配位的硝酸根中的 4个氧原子 ,以及 1个水分子的氧原子配位 ,构成 1个九配位的单帽四方反棱柱体 ;配阴离子中 ,1个Th4+ 与 6个双齿配位的硝酸根离子配位

【Abstract】 A thorium(Ⅳ) nitrate complex with phosphinoxide[-CH 2P(O)Ph 2]-substituted calixarene [L·ThOH 2(NO 3) 2][Th(NO 3) 6]·CH 3CN has been prepared and characterized by elemental analysis and IR spectroscopy. Its crystal structure was determined by X-ray diffraction method. It belongs to triclinic crystal system, space group P 1, with a=1.990(7) nm, b=2.217(8) nm, c=2.890(10) nm; α=104.92(12)°, β=100.76(14)°, γ=93.13(10)°, Z=4, V=12.033(7) nm 3, R 1=0.0901, wR 2=0.1907. The complex consists of a coordination cation and a coordination anion. In the cation the thorium(Ⅳ) is coordinated to the four phosphinoxide oxygen atoms of the calixarene, four oxygen atoms from two bidentate nitrate anions and one oxygen from a water molecule forming a nine-coordinate monocapped square antiprism. In the coordination anion, the thorium(Ⅳ) is coordinated to six bidentate nitrate. In addition, an acetonitrile molecule was encapsulated in the cavity of calixarene.

  • 【文献出处】 化学学报 ,Acta Chimica Sinica , 编辑部邮箱 ,2004年13期
  • 【分类号】O641.4
  • 【被引频次】15
  • 【下载频次】181
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