[(thf)₄Ca(PPh₂)₂] | 1314701-90-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [(thf)₄Ca(PPh₂)₂]
• 英文别名: [(THF)4Ca(PPh2)2]；calcium;diphenylphosphanide;oxolane
• CAS: 1314701-90-0；960589-67-7
• 化学式: C₄₀H₅₂CaO₄P₂
• 分子量: 698.876
• InChiKey: VWFIJWHJGVOZNZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.97
• 重原子数：
  47
• 可旋转键数：
  4
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  [(thf)₄Ca(PPh₂)₂] 在 selenium 作用下， 以 四氢呋喃 为溶剂， 反应 6.0h， 以81%的产率得到[(thf)2Ca(Se2PPh2)2]
  参考文献：
  名称：

  Oxidation Products of Calcium and Strontium Bis(diphenylphosphanide)

  摘要：

  The tetrahydrofuran adducts [(thf)(4)M(PPh2)(2)] (M = Ca, Sr) are air sensitive and can easily be oxidized by chalcogens. Metalation of diphenylphosphane oxide, diphenylphosphinic acid, and diphenyldithiophosphinic acid as well as salt metathetical approaches of the potassium salts with MI2 allow the synthesis of [(thp(4)Ca(OPPh2)(2)i (1), [(dmso)(2)Ca-(O2PPh2)2] (2), [thf)(3)Ca(O2PPh2)I](2) (3), [(thf)(3)Ca(S2PPh2)(2)] (4), [(thf(2))Ca(Se2PPh2)(2)] (5), [(thf)(3)Sr(S2PPh2)(2)] (6), [(thf)(3)Sr(Se2PPh2)(2)] (7), and [(thf)(2)Ca(O2PPh2)(S2PPh2)](2) (8), respectively. The diphenylphosphinite anion in 1 contains a phosphorus atom in a trigonal pyramidal environment and binds terminally via the oxygen atom to calcium. The diphenylphosphinate anions act as bridging ligands leading to polymeric structures of calcium bis(diphenylphosphinates). Therefore strong Lewis bases such as dimethylsulfmdde (dmso) are required to recrystallize this complex yielding chain-like 2. The chain structure can also be cut into smaller units by ligands which avoid bridging positions such as iodide and diphenyldithiophosphinate (3 and 8, respectively). In general, diphenyldithio- and -diselenophosphinate anions act as terminal ligands and allow the isolation of mononuclear complexes 4 to 7. In these molecules the alkaline earth metals show coordination numbers of six (5) and seven (4, 6, and 7).

  DOI：

  10.1021/ic300975s
• 作为产物：
  描述：

  二苯基氯化膦 在 盐酸 、 水 作用下， 以 氘代四氢呋喃 为溶剂， 生成 [(thf)₄Ca(PPh₂)₂]
  参考文献：
  名称：

  钙介导的有机异氰酸酯与二苯膦氧化物的加氢磷酸化反应

  摘要：

  钙介导的二苯基膦氧化物在有机异氰酸酯和异硫氰酸酯中的加成反应生成N-烷基和N-芳基取代的二苯基磷酰基甲酰胺（E = O，R =  i Pr，t Bu，c Hex，Ph，C 6 H 4 -4-Br， C 6 H 2 -2,4,6 -Me 3和Naph）和-硫代甲酰胺（E = S，R =  i Pr，c Hex，Ph和C 6 H 4 -4-Me） Ph 2型P（O）–C（E）–N（H）R。所有衍生物都通过IR和NMR光谱以及X射线衍射实验进行了表征。对于硫代类似物和N-芳基取代基，NH拉伸模式的波数较小。在固态下，所有甲酰胺和硫代甲酰胺都通过N–H⋯O–P氢桥形成二聚体。与P–C Ph距离相比，P–C CE键显着延长。

  DOI：

  10.1071/ch13259
• 作为试剂：
  描述：

  环己基异氰酸酯 、 Diphenylphosphine oxide 在 [(thf)₄Ca(PPh₂)₂] 作用下， 以 四氢呋喃 为溶剂， 反应 24.25h， 以70%的产率得到N-cyclohexyl-(diphenylphosphoryl)formamide
  参考文献：
  名称：

  钙介导的有机异氰酸酯与二苯膦氧化物的加氢磷酸化反应

  摘要：

  钙介导的二苯基膦氧化物在有机异氰酸酯和异硫氰酸酯中的加成反应生成N-烷基和N-芳基取代的二苯基磷酰基甲酰胺（E = O，R =  i Pr，t Bu，c Hex，Ph，C 6 H 4 -4-Br， C 6 H 2 -2,4,6 -Me 3和Naph）和-硫代甲酰胺（E = S，R =  i Pr，c Hex，Ph和C 6 H 4 -4-Me） Ph 2型P（O）–C（E）–N（H）R。所有衍生物都通过IR和NMR光谱以及X射线衍射实验进行了表征。对于硫代类似物和N-芳基取代基，NH拉伸模式的波数较小。在固态下，所有甲酰胺和硫代甲酰胺都通过N–H⋯O–P氢桥形成二聚体。与P–C Ph距离相比，P–C CE键显着延长。

  DOI：

  10.1071/ch13259

文献信息

• Coordination Behavior and Coligand‐Dependent <i>cis</i> / <i>trans</i> Isomerism of Calcium Bis(diphenylphosphanides)
  作者：Jens Langer、Tareq M. A. Al‐Shboul、Fadi M. Younis、Helmar Görls、Matthias Westerhausen

  DOI：10.1002/ejic.201100241

  日期：2011.7

  solution, a fast equilibrium converts these isomers into each other leading to a single set of resonances in the NMR spectra. The THF ligands can be replaced by stronger Lewis bases, such as N-methylimidazole (MeIm), which leads to the formation of [(MeIm)4Ae(PPh2)2] [Ae = Ca (2a), Sr (2b)]. The use of tetradentate hexamethyltriethylenetetramine (hmteta) fixes a cis configuration yielding [(hmteta)Ca(PPh2)2]

  KPPh2 与 CaI2 和 SrI2 在 THF 中的盐复分解反应产生相应的复合物 [(THF)4Ae(PPh2)2] [Ae = Ca (1), Sr]。根据结晶条件，可以分离顺式或反式 [(THF)4Ca(PPh2)2]。在溶液中，快速平衡将这些异构体相互转化，从而在 NMR 光谱中产生一组共振。THF 配体可以被更强的路易斯碱取代，例如 N-甲基咪唑 (MeIm)，这会导致形成 [(MeIm)4Ae(PPh2)2] [Ae = Ca (2a), Sr (2b)]。四齿六甲基三亚乙基四胺 (hmteta) 的使用固定了顺式构型，产生 [(hmteta)Ca(PPh2)2] (3)。所有化合物对空气和湿气都非常敏感，因此还获得了部分氧化产物 [(hmteta)Ca(PPh2)(OPPh2)] (4) 的一些晶体。
• Calcium-mediated Hydrophosphorylation of Organic Isocyanates with Diphenylphosphane Oxide
  作者：Stephan Härling、Julia Greiser、Tareq M. A. Al-Shboul、Helmar Görls、Sven Krieck、Matthias Westerhausen

  DOI：10.1071/ch13259

  日期：——

  The calcium-mediated addition of diphenylphosphane oxide to organic isocyanates and isothiocyanates yields N-alkyl and N-aryl substituted diphenylphosphorylformamides (E = O, R = iPr, tBu, cHex, Ph, C6H4-4-Br, C6H2-2,4,6-Me3, and Naph) and -thioformamides (E = S, R = iPr, cHex, Ph, and C6H4-4-Me), respectively, of the type Ph2P(O)–C(E)–N(H)R. All derivatives were characterized by IR and NMR spectroscopy

  钙介导的二苯基膦氧化物在有机异氰酸酯和异硫氰酸酯中的加成反应生成N-烷基和N-芳基取代的二苯基磷酰基甲酰胺（E = O，R =  i Pr，t Bu，c Hex，Ph，C 6 H 4 -4-Br， C 6 H 2 -2,4,6 -Me 3和Naph）和-硫代甲酰胺（E = S，R =  i Pr，c Hex，Ph和C 6 H 4 -4-Me） Ph 2型P（O）–C（E）–N（H）R。所有衍生物都通过IR和NMR光谱以及X射线衍射实验进行了表征。对于硫代类似物和N-芳基取代基，NH拉伸模式的波数较小。在固态下，所有甲酰胺和硫代甲酰胺都通过N–H⋯O–P氢桥形成二聚体。与P–C Ph距离相比，P–C CE键显着延长。
• Oxidation Products of Calcium and Strontium Bis(diphenylphosphanide)
  作者：Tareq M. A. Al-Shboul、Gritt Volland、Helmar Görls、Sven Krieck、Matthias Westerhausen

  DOI：10.1021/ic300975s

  日期：2012.7.16

  The tetrahydrofuran adducts [(thf)(4)M(PPh2)(2)] (M = Ca, Sr) are air sensitive and can easily be oxidized by chalcogens. Metalation of diphenylphosphane oxide, diphenylphosphinic acid, and diphenyldithiophosphinic acid as well as salt metathetical approaches of the potassium salts with MI2 allow the synthesis of [(thp(4)Ca(OPPh2)(2)i (1), [(dmso)(2)Ca-(O2PPh2)2] (2), [thf)(3)Ca(O2PPh2)I](2) (3), [(thf)(3)Ca(S2PPh2)(2)] (4), [(thf(2))Ca(Se2PPh2)(2)] (5), [(thf)(3)Sr(S2PPh2)(2)] (6), [(thf)(3)Sr(Se2PPh2)(2)] (7), and [(thf)(2)Ca(O2PPh2)(S2PPh2)](2) (8), respectively. The diphenylphosphinite anion in 1 contains a phosphorus atom in a trigonal pyramidal environment and binds terminally via the oxygen atom to calcium. The diphenylphosphinate anions act as bridging ligands leading to polymeric structures of calcium bis(diphenylphosphinates). Therefore strong Lewis bases such as dimethylsulfmdde (dmso) are required to recrystallize this complex yielding chain-like 2. The chain structure can also be cut into smaller units by ligands which avoid bridging positions such as iodide and diphenyldithiophosphinate (3 and 8, respectively). In general, diphenyldithio- and -diselenophosphinate anions act as terminal ligands and allow the isolation of mononuclear complexes 4 to 7. In these molecules the alkaline earth metals show coordination numbers of six (5) and seven (4, 6, and 7).