(CH2(Me)NPtBu2)2 | 1148013-33-5

• 分子结构分类: 有机化合物 - 有机磷化合物
• 英文名称: (CH2(Me)NPtBu2)2
• 英文别名: (CH2NMePtBu2)2；N,N'-bis(ditert-butylphosphanyl)-N,N'-dimethylethane-1,2-diamine
• CAS: 1148013-33-5
• 化学式: C₂₀H₄₆N₂P₂
• 分子量: 376.546
• InChiKey: OVVLMVFHTRDSFP-UHFFFAOYSA-N

物化性质

• 沸点：
  418.3±55.0 °C(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  24
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  氯化镍二甲氧基乙烷 、 (CH2(Me)NPtBu2)2 以 四氢呋喃 为溶剂， 以95%的产率得到[((t-Bu)2P(H)N(Me)CHCH2N(Me)P(t-Bu)2)NiCl3]
  参考文献：
  名称：

  Nickel(II) and Palladium(II) Bis-Aminophosphine Pincer Complexes

  摘要：

  The aminophosphine ligands CH2(CH2NHPtBu2)(2) (1), (CH2NHPtBu2)(2) (2), and (CH2NMePtBu2)(2) (3) were prepared from the corresponding amines and ClPtBu2. The ligand 1 reacts with PdI2 to give the pincer complex (kappa P-3,C,P-CH(CH2NHPtBu2)(2))PdI (4). The analogous reaction of 1 with NiCl2(dme) gave a the purple product (kappa P-3,N,P-tBu(2)PNH(CH2)(3)NPtBu2)NiCl (5), which contains a strained three-membered P-N-Ni ring. Subsequent reaction of 5 with B(C6F5)(3) resulted in conversion to (kappa P-3,C,P-CH(CH2NHPtBu2)(2))NiCl (6). The related reaction of the aminophosphine ligand 2 with PdI2 and with NiCl2(dme) led, in both cases, to the complexes (kappa P-3,N, P-tBu(2)PNH(CH2)(2)NPtBu2)MX (MX = PdI (7), NiCl (8)), respectively, whereas the reaction of 3 with PdX2 gave (kappa P-3,C, P-tBu(2)PN(Me)CHCH2N(Me)PtBu2)PdX (X = I(9), Br (10), Cl (11)). The analogous reaction of 3 with NiCl2(dme) afforded [(tBu(2)PH)(NMe)(CH2)(2)(NMe)(tBu(2)P)NiCl3], (12), which upon treatment with B(C6F5)(3) afforded the species (kappa P-3,C, P-tBu(2)PN(Me)CHCH2N(Me)PtBu2)NiCl (13). Crystallographic studies of 4-6, 8, 9, 11, and 12 are reported. The implications of these results are considered.

  DOI：

  10.1021/om200439q
• 作为产物：
  描述：

  二叔丁基氯化膦 、 N,N'-二甲基乙二胺 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 以86%的产率得到(CH2(Me)NPtBu2)2
  参考文献：
  名称：

  Titanium complexes of amidophosphinimide ligands

  摘要：

  将三元膦 MeC(CH2NMe)3P 和 N(CH2CH2NMe)3P 转化为相应的膦亚胺，并制备出相应的钛络合物 MeC(CH2NMe)3PNTiCpCl2 (2) 和 N(CH2CH2NMe)3PNTiCpCl2 (5)。这些物质还被烷基化，得到相应的二甲基衍生物。初步尝试将这些衍生物用于以 MAO 为活化剂的乙烯聚合反应，结果发现它们的活性几乎可以忽略不计。我们开发了一种利用双膦亚胺 (CH2(Me)NPtBu2)2 的替代合成方法来制备 (CH2(Me)NP(tBu2)NSiMe3)2 (8)、(CH2(Me)NP(tBu2)NH)2(9)，随后又制备了[(CH2(Me)NP(tBu2)N)2]Ti(NMe2)2(10)、[(CH2(Me)NP(tBu2)N)2]TiCl2(11) 和[(CH2(Me)NP(tBu2)N)2]TiMe2(12)。为便于比较，还制备了相关的 [tBu2(Me2N)PN]2TiCl2 (14) 和 [tBu2(Me2N)PN]2TiMe2 (15)。化合物 (12) 和 (15) 使用 2 等量的 [Ph3C][B(C6F5)4] 作为活化剂，具有中等至良好的聚合活性。

  DOI：

  10.1039/b816184d

文献信息

• Titanium complexes of amidophosphinimide ligands
  作者：Osamah Alhomaidan、Chad Beddie、Guangcai Bai、Douglas W. Stephan

  DOI：10.1039/b816184d

  日期：——

  The tripodal phosphines MeC(CH2NMe)3P and N(CH2CH2NMe)3P were converted to the corresponding phosphinimines and the corresponding Ti-complexes MeC(CH2NMe)3PNTiCpCl2 (2) and N(CH2CH2NMe)3PNTiCpCl2 (5) were prepared. These species were also alkylated to give the corresponding dimethyl derivatives. Preliminary attempts to utilize these species in the polymerization of ethylene with MAO as the activator resulted in all but negligible activity. An alternative synthetic approach utilizing the bis-phosphinimine (CH2(Me)NPtBu2)2 was developed to prepare (CH2(Me)NP(tBu2)NSiMe3)2 (8), (CH2(Me)NP(tBu2)NH)2 (9) and subsequently [(CH2(Me)NP(tBu2)N)2]Ti(NMe2)2 (10), [(CH2(Me)NP(tBu2)N)2]TiCl2 (11) and [(CH2(Me)NP(tBu2)N)2]TiMe2 (12). For comparison purposes the related species [tBu2(Me2N)PN]2TiCl2 (14) and [tBu2(Me2N)PN]2TiMe2 (15) were also prepared. Compounds (12) and (15), using 2 equiv. of [Ph3C][B(C6F5)4] as the activator, resulted in moderate to good polymerization activities.

  将三元膦 MeC(CH2NMe)3P 和 N(CH2CH2NMe)3P 转化为相应的膦亚胺，并制备出相应的钛络合物 MeC(CH2NMe)3PNTiCpCl2 (2) 和 N(CH2CH2NMe)3PNTiCpCl2 (5)。这些物质还被烷基化，得到相应的二甲基衍生物。初步尝试将这些衍生物用于以 MAO 为活化剂的乙烯聚合反应，结果发现它们的活性几乎可以忽略不计。我们开发了一种利用双膦亚胺 (CH2(Me)NPtBu2)2 的替代合成方法来制备 (CH2(Me)NP(tBu2)NSiMe3)2 (8)、(CH2(Me)NP(tBu2)NH)2(9)，随后又制备了[(CH2(Me)NP(tBu2)N)2]Ti(NMe2)2(10)、[(CH2(Me)NP(tBu2)N)2]TiCl2(11) 和[(CH2(Me)NP(tBu2)N)2]TiMe2(12)。为便于比较，还制备了相关的 [tBu2(Me2N)PN]2TiCl2 (14) 和 [tBu2(Me2N)PN]2TiMe2 (15)。化合物 (12) 和 (15) 使用 2 等量的 [Ph3C][B(C6F5)4] 作为活化剂，具有中等至良好的聚合活性。
• Nickel(II) and Palladium(II) Bis-Aminophosphine Pincer Complexes
  作者：Erin A. Gwynne、Douglas W. Stephan

  DOI：10.1021/om200439q

  日期：2011.8.8

  The aminophosphine ligands CH2(CH2NHPtBu2)(2) (1), (CH2NHPtBu2)(2) (2), and (CH2NMePtBu2)(2) (3) were prepared from the corresponding amines and ClPtBu2. The ligand 1 reacts with PdI2 to give the pincer complex (kappa P-3,C,P-CH(CH2NHPtBu2)(2))PdI (4). The analogous reaction of 1 with NiCl2(dme) gave a the purple product (kappa P-3,N,P-tBu(2)PNH(CH2)(3)NPtBu2)NiCl (5), which contains a strained three-membered P-N-Ni ring. Subsequent reaction of 5 with B(C6F5)(3) resulted in conversion to (kappa P-3,C,P-CH(CH2NHPtBu2)(2))NiCl (6). The related reaction of the aminophosphine ligand 2 with PdI2 and with NiCl2(dme) led, in both cases, to the complexes (kappa P-3,N, P-tBu(2)PNH(CH2)(2)NPtBu2)MX (MX = PdI (7), NiCl (8)), respectively, whereas the reaction of 3 with PdX2 gave (kappa P-3,C, P-tBu(2)PN(Me)CHCH2N(Me)PtBu2)PdX (X = I(9), Br (10), Cl (11)). The analogous reaction of 3 with NiCl2(dme) afforded [(tBu(2)PH)(NMe)(CH2)(2)(NMe)(tBu(2)P)NiCl3], (12), which upon treatment with B(C6F5)(3) afforded the species (kappa P-3,C, P-tBu(2)PN(Me)CHCH2N(Me)PtBu2)NiCl (13). Crystallographic studies of 4-6, 8, 9, 11, and 12 are reported. The implications of these results are considered.