NH4Se2P(O(2)Bu)2 | 881008-69-1

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: NH4Se2P(O(2)Bu)2
• CAS: 881008-69-1
• 化学式: C₈H₁₈O₂PSe₂*H₄N
• 分子量: 353.162
• InChiKey: WFINKEIIYYTYJL-WSZWBAFRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.01
• 重原子数：
  14.0
• 可旋转键数：
  6.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  54.96
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  tetrakis(acetonitrile)silver(I) hexafluorophosphate 、 NH4Se2P(O(2)Bu)2 、 四丁基碘化铵 以 二氯甲烷 为溶剂， 以55%的产率得到[Ag11(μ9-Se)(μ3-I)3(Se2P(O(2)Bu)2)6]
  参考文献：
  名称：

  Selenium-Centered, Undecanuclear Silver Cages Surrounded by Iodo and Dialkyldiselenophosphato Ligands. Syntheses, Structures, and Photophysical Properties

  摘要：

  Three clusters [Ag-11(mu(9)-Se)(mu(3)-I)(3){Se2P(OR)(2)}(6)] (R = Et, 1; Pr-i, 2; Bu-2, 3) were isolated from the reaction of [Ag(CH3CN)(4)](PF6), NH4[Se2P(OR)(2)], and Bu4NI in a molar ratio of 4:3:1 in CH2Cl2 in 47-55% yield. Compounds 1 and 2 can also be synthesized with high yield from the reaction of Ag-10(Se)[Se2P(OR)(2)](8) with 8 equiv of Bu4NI. In the positive fast atom bombardment mass spectra of 1-3, two major peaks that correspond to the intact molecule with the loss of an iodide ion, [Ag-11(mu(9)-Se)(mu(3)-I)(2){Se2P(OR)(2)}(6)](+), and a diselenophosphate ligand, [Ag-11(mu(9)-Se)(mu(3)-I)(3){Se2P(OR)(2)}(5)](+), were identified. Single-crystal X-ray analyses of 2 and 3 reveal an Ag11Se core stabilized by three iodide anions and six diselenophosphato ligands in a tetrametallic tetraconnective (mu(2),mu(2)) coordination mode. The central core adopts the geometry of a 3,3,4,4,4-pentacapped trigonal prism with a selenium atom in the center. In addition, weak intermolecular Se center dot center dot center dot I interactions exist in 2 and form a one-dimensional polymeric chain structure. Furthermore, all compounds exhibit orange-red luminescence in both the solid state and solution.

  DOI：

  10.1021/ic052015+

文献信息

• Structure, Photophysical Properties, and DFT Calculations of Selenide-Centered Pentacapped Trigonal Prismatic Silver(I) Clusters
  作者：C. W. Liu、Ching-Shiang Feng、Rei-Jen Fu、Hao-Wei Chang、Jean-Yves Saillard、Samia Kahlal、Ju-Chun Wang、I-Jy Chang

  DOI：10.1021/ic902571q

  日期：2010.6.7

  Undecanuclear silver clusters [Ag(11)(mu(g)-Se)(mu(3)-Br)(3)Se(2)P(OR)(2)}(6)] (R = Et, (1)Pr, (2)Bu) were isolated from the reaction of [Ag(CH(3)CN)(4)](PF(6)), NH(4)[Se(2)P(OR)(2)], and Bu(4)NBr in a molar ratio of 4:3:1 in CH(2)Cl(2) at -20 degrees C. Clusters were characterized by elemental analysis, NMR spectroscopy ((1)H, (31)P, and (77)Se), positive FAB mass spectrometry, and X-ray crystallography of the isopropyl derivative, Structural elucidations revealed that the Ag(11)Se core geometry of clusters is a selenide-centered, slightly distorted 3,3,4,4,4-pentacapped trigonal prism surrounded by six diselenophosphato ligands, each in a tetrametallic tetraconnective (mu(2),mu(2)) coordination mode, and three mu(3)-bromide anions. All compounds exhibited orange luminescence both as a solid and in solution. The electronic structure of these clusters was studied by DFT calculations, and their optical properties were rationalized through a TDDFT investigation. The computed metrical parameters of the clusters were consistent with the corresponding X-ray data of [Ag(11)(mu g-Se)(mu(3)-Br)(3)Se(2)P(O(i)Pr)(2)}(6)]. The theoretical investigations affirmed that the low-energy absorptions as well as emissions were due to transitions from an orbital mostly of a selenophosphate ligand/central Se atom character to an orbital of metal character.