tetrakis[bis(2-dimethylphosphinoethyl)-phosphido]thorium(IV) | 145329-04-0

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: tetrakis[bis(2-dimethylphosphinoethyl)-phosphido]thorium(IV)
• 英文别名: bis(2-dimethylphosphanylethyl)phosphanide;thorium(4+)
• CAS: 145329-04-0；164713-07-9
• 化学式: C₃₂H₈₀P₁₂Th
• 分子量: 1068.71
• InChiKey: ISZLWKBCSIRGRJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.66
• 重原子数：
  45
• 可旋转键数：
  12
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tetrakis[bis(2-dimethylphosphinoethyl)-phosphido]thorium(IV) 、 一氧化碳 以 甲苯 为溶剂， 以73%的产率得到
  参考文献：
  名称：

  螯合二膦基膦酸酯配体的同化Act系元素配合物：与一氧化碳反应的新模式和U {P（CH2CH2PMe2）2} 4的X射线晶体结构

  摘要：

  The tetrakis(dialkylphosphido) complexes M{P(CH(2)CH(2)PMe(2))(2)}(4) (M = Th, U) are isolated in high yield from the reaction of MCl(4) with 4 mol equiv of (Li+ or K+)P--(CH(2)CH(2)PMe(2))(2) ((Li/K)PPP). The uranium and thorium compounds are isostructural, although the thorium compound exhibits dimorphism. Detailed shape analysis indicates the structures of the three tetraphosphides conform to triangulated dodecahedra distorted toward bicapped trigonal prisms. The thorium compound is shown to be labile, exhibiting facile exchange of coordinated with uncoordinated tertiary phosphine functions, by P-31{H-1} NMR spectroscopy The thorium compound reacts readily with CO to give a unique double-insertion product where CO is incorporated into a diphosphacarbinol (diphospha secondary alcohol) derivative with two phosphido phosphorus atoms becoming bonded to the inserted carbon atom and the new P2CO unit being eta(3)-bonded to thorium. Structural and spectroscopic data indicate a reduction in C-O bond order from 3 to 1 upon insertion. Hydrolysis liberates the free diphospha secondary alcohol, which is unstable with respect to P-C cleavage and aldehyde formation under mass-spectroscopic conditions. Alkenes with vinylic protons and phenols also react with the thorium tetraphosphide, which eliminates HPPP. The new compounds were characterized by analytical and spectroscopic techniques and by X-ray crystallography for the uranium complex.

  DOI：

  10.1021/om00008a012
• 作为产物：
  描述：

  bis(2-dimethylphosphinoethyl)phosphidolithium 、 氯化钍 以 not given 为溶剂， 生成 tetrakis[bis(2-dimethylphosphinoethyl)-phosphido]thorium(IV)
  参考文献：
  名称：

  四磷th配合物Th [P（CH 2 CH 2 PMe 2）2 ] 4的合成和晶体结构，only配合物仅具有金属-磷配体键

  摘要：

  LiP（CH 2 CH 2 PMe 2）2与ThCl 4的反应生成第一act系四磷酸配合物Th [P（CH 2 CH 2 PMe 2）2 ] 4；仅与磷配体结合的一类f元素络合物的第一成员，并针对其进行了光谱，分析和X射线晶体学表征。

  DOI：

  10.1039/c39920001469