[Li₂(o-C₆H₄PPh₂NPh)₂]OEt₂ | 663627-50-7

• 英文名称: [Li₂(o-C₆H₄PPh₂NPh)₂]OEt₂
• 英文别名: [Li(o-C6H4(phenyl)2PN(phenyl)]2(diethyl ether)
• CAS: 663627-50-7
• 化学式: C₅₂H₄₈Li₂N₂OP₂
• 分子量: 792.795
• InChiKey: GULSZACLVFUEFJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 [Li₂(o-C₆H₄PPh₂NPh)₂]OEt₂ 以 四氢呋喃 为溶剂， 以67%的产率得到Ir(cyclooctadiene)(o-C6H4P(phenyl)2N(phenyl))
  参考文献：
  名称：

  Anionic Phosphinimine-Chelate Complexes of Rhodium and Iridium:  Steric and Electronic Influences on Oxidative Addition of CH₂Cl₂

  摘要：

  The phosphinimines Ph3PNR (R = Ph 1, 2,6-Me2C6H3 2, 3,5-Me2C6H3 3, 2,6-i-Pr2C6H3 4) were prepared and used to generate the species of the form [Li(o-C6H4PPh2NR)](2).Et2O (R = Ph 5, 2,6-Me2C6H3 6, 3,5-Me2C6H3 7, 2,6-i-Pr2C6H3 8). Subsequent reactions with [Rh(mu-Cl)(COD)](2) gave the complexes Rh(COD)(o-C6H4PPh2NR) (R = Ph 9, 2,6-Me2C6H3 10, 3,5-Me2C6H3 11, 2,6-i-Pr2C6H3 12). Similarly, the Ir analogue of 9 (13) was prepared using [Ir(mu-Cl)(COD)](2). The reaction of 9 with (CH2PPh2)(2) afforded Rh(PPh2CH2CH2PPh2)(o-C6H4PPh2NPh) (14). Compound 9 was also shown to react with CH2Cl2 to give two products, one of which was confirmed to be [Rh(o-C6H4PPh2NPh)(CH2-o-C6H4PPh2NPh)(mu-Cl)(2)Rh(COD)] (15). Similar treatment of 10 and 12 with CH2Cl2 showed no reaction, while reaction of 11 with CH2Cl2 gave a mixture of unidentified products. The related imidazole-phosphinimine ligands (N2C3H3)PPh2NR (R = Ph 18, 2,6-Me2C6H3 19) were also prepared. These ligands react with NaH to give the corresponding Na-imidazolate-phosphinimines, 20 and 21, and subsequent reaction with [Rh(mu-Cl)(COD)](2) gave the complexes Rh(COD)((N2C3H2)PPh2NR) (R = Ph 22, 2,6-Me2C6H3 23). The compounds 22 and 23 do not react with CH2Cl2. The effects of steric and electronic modifications to the ligands on oxidative addition of C - Cl bonds are discussed. DFT calculations were performed on the model fragments [Rh((C6H4)PH2NH)] and [Rh((N2C3H2)PH2NH)], and the calculated atomic charges provide some insight into the reactivity of these compounds.

  DOI：

  10.1021/om030539g
• 作为产物：
  描述：

  乙醚 、 苯基锂 、 四苯基氨化膦 生成 [Li₂(o-C₆H₄PPh₂NPh)₂]OEt₂
  参考文献：
  名称：

  亚氨基正膦生成的Pd（II）和Pd（IV）的双环金属配合物：合成，结构和反应性

  摘要：

  单核双原钯配合物[Pd（CˆN）{C 6 H 4（PPh 2 NPh）-2}] [CˆN =（2-（吡啶-2-基）苯基）3a，（2-（（二甲基氨基）甲基基）苯基）3B，（S） - （2-（1-（二甲基氨基）乙基）苯基）3c中，（喹啉-8-基甲基）3D，（4-甲氧基-2 - （（三苯基-λ 5 -phosphanylidene）氨基甲酰基）苯基）3e ]已通过相应的氯化物二聚体[Pd（μ-Cl）（CˆN）] 2（1a – 1e）与锂衍生物[Li {C 6 H 4（PPh 2NPh）-2}]（2）在Et 2 O中。光谱数据表明，两个有palpalated的C原子处于顺式位置，这由3a的X射线结构证实。用PhI（OAc）2氧化3a得到相应的Pd（IV）衍生物（OC-6-32）[Pd（OAc）2 {C 6 H 4（PPh 2 NPh）-2} {C 6 H 4-（ 2'-NC 5 H 4）-2}]

  DOI：

  10.1016/j.jorganchem.2014.05.024

文献信息

• Metallated triphenylphosphinimine complexes
  作者：Pingrong Wei、Katie T. K. Chan、Douglas W. Stephan

  DOI：10.1039/b305877h

  日期：——

  The reagent [(o-C6H4PPh2NSiMe3)Li]2·Et2O 1 reacted with BCl3 affording (o-C6H4PPh2NSiMe3)BCl24. Similarly reaction of 1 with Me2AlCl resulted in a 1 ∶ 1 mixture of (o-C6H4PPh2NSiMe3)AlMe25 and (o-C6H4PPh2NSiMe3)Al(Me)Cl 6 while the analogous reaction of 1 with GaCl3 gave (o-C6H4PPh2NSiMe3)2Ga(o-C6H4PPh2NH) 7. The analogous compound [Li(o-C6H4PPh2NPh)]2·Et2O 2 was used to make (o-C6H4PPh2NPh)GaCl28, while reaction of 2 with Me2AlCl gave a mixture of [(o-C6H4PPh2NPh)AlCl29 and the salt [(o-C6H4PPh2NPh)2Al][AlMeCl3] 10. The compound 2 also reacts with PdCl2(COD) affording [Pd(o-C6H4PPh2NPh)(μ-Cl)]211 and [Pd(o-C6H4PPh2NPh)2] 12. Similarly, the complexes [Ni(o-C6H4PPh2NPh)2] 13 and [Ni(o-C6H4PPh2N(3,5-C6H3Me2))2] 14 were prepared. The compounds 4–14 have been structurally characterized by X-ray methods.

  试剂[(o-C6H4PPh2NSiMe3)Li]2·Et2O 1 与BCl3反应，得到(o-C6H4PPh2NSiMe3)BCl24。 1 与 Me2AlCl 的类似反应产生 (o-C6H4PPh2NSiMe3)AlMe25 和 (o-C6H4PPh2NSiMe3)Al(Me)Cl 6 的 1 ∶ 1 混合物，而 1 与 GaCl3 的类似反应产生 (o-C6H4PPh2NSiMe3)2Ga(o- C6H4PPh2NH) 7. 类似化合物[Li(o-C6H4PPh2NPh)]2·Et2O 2 用于制备(o-C6H4PPh2NPh)GaCl28，而2与Me2AlCl反应得到[(o-C6H4PPh2NPh)AlCl29和盐[( o-C6H4PPh2NPh)2Al][AlMeCl3] 10. 化合物 2 也与 PdCl2(COD) 反应，得到 [Pd(o-C6H4PPh2NPh)(μ-Cl)]211 和 [Pd(o-C6H4PPh2NPh)2] 12. 同样，配合物 [Ni(o-C6H4PPh2NPh)2] 13和[Ni(o-C6H4PPh2N(3,5-C6H3Me2))2] 准备了14个。化合物4-14已通过X射线方法进行了结构表征。