[o-(Ph2PCH2P(Ph)2N)C6H4N(CH)2N(CH2Ph)CH]Br | 1196117-31-3

• 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: [o-(Ph2PCH2P(Ph)2N)C6H4N(CH)2N(CH2Ph)CH]Br
• CAS: 1196117-31-3
• 化学式: Br*C₄₁H₃₆N₃P₂
• 分子量: 712.608
• InChiKey: DRANEEKHGGBAHX-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  5.39
• 重原子数：
  47.0
• 可旋转键数：
  10.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  21.17
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  p-叠氮甲苯 、 [o-(Ph2PCH2P(Ph)2N)C6H4N(CH)2N(CH2Ph)CH]Br 、 双二苯基膦甲烷 以 二氯甲烷 为溶剂， 以86%的产率得到
  参考文献：
  名称：

  Synthesis and characterization of zinc complexes supported by NHC-based CNN- and CNP-tridentate ligands and their catalysis in the ring-opening polymerization of rac-lactide and ε-caprolactone

  摘要：

  A series of zinc complexes bearing NHC-based C,N,N- or C,N,P-tridentate ligands were synthesized and characterized and the catalysis of the complexes toward the ring-opening polymerization of rac-lactide was evaluated. The ligand precursors [2-(CHN(R)(CH)(2)N)C6H4N=P(Pb)(2)CH2(Ph)(2)CH2Py](+) I- (2a, R = Me; 2b, R = iPr) prepared from [2-N3C6H4(N(CH)(2)N(R)CH)](+) I- (R = Me or iPr) and Ph2PCH2Py were successively treated with nBuLi and ZnEt2 to afford corresponding zinc complexes [Zn(Et){2-(CN(R)(CH)(2)N)(C6H4NP(Ph)(2)=CHpy}] (3a, R = Me; 3b, R = iPr). Similar treatment of [2-(CHN(Me)(CH)(2)N)C6H4N P(Ph)(2)CH2PPh2]I-+(-) (4a) (prepared from [2-N3C6H4(N(CH)(2)N(Me)CH)(+) I- and Ph2PCH2PPh2) with nBuLi and then ZnEt2 gave [Zn(Et){2-(CN(Me)(CH)(2)N)C6H4NP(Ph)(2)=CHPPh2)] (5). Treatment of [2-(CHN(R)(CH2N)C6H4N-P(Ph)(2)CH2PPh2]X-+(-) (4a, R = Me, X = l; 4h, R = Bn, X = Br; 4c, R = iPr, X = l) with p-MeC6H4N3 resulted in [2-(CHN(R)(CH)(2)N)C6H4N P(Ph)(2)CH2F(Ph)(2)=N(p-MeC6H4)(+) X-(6a, R = Me, X = l; 6b, R = Bn, X = Br; 6c, R = iPr, X = l). The reaction of 6a with nBuLi and ZnEt2 in sequence produced IZn(Et){2-(CN(Me)(CH)(2)N)C6H4NP(Ph)(2)=C1IP(Ph)(2)=N(p-McC(6)H(4))}1 (7). Whereas the reaction of 6a c with an equimolar amount of ZnEt2 gave [Zn(X){2-(ON(R)(CH)(2))C6H4NP(Ph)(2)=CHP(Ph)(2)=N(p-MeC6H4)}1(8a, R = Me, X = l; 8b, R = Bn, X = Br; 8c, R = iPr, X = l). All new compounds were characterized by H-1, C-13 and P-31 NMR spectroscopy and elemental analyses. The structures of complexes 3a, 5 and 8b were additionally characterized by single crystal X-ray diffraction. In the presence of BnOH complexes 3a, 3b, 5 and 7 catalyze the ring-opening polymerization of rac-lactide at room temperature and 3a, 3b, and 5 exhibited high activity. Complexes 8a c are inactive under the same conditions. Complexes 3a and 5 were also tested for the catalysis in the ROP of epsilon-caprolactone and both showed good catalytic activity. (C) 2015 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2015.02.013

文献信息

• N-Heterocyclic Carbene-Based Nickel Complexes: Synthesis and Catalysis in Cross-Couplings of Aryl Chlorides with ArMX (M = Mg or Zn)
  作者：Cheng Zhang、Zhong-Xia Wang

  DOI：10.1021/om9006399

  日期：2009.11.23

  LiBun. C,N,P-Chelate nickel complex [Ni(Br)2-(CN(CH2Ph)(CH)2N)C6H4N═P(Ph2)CH2PPh2}]+Br− was obtained by a similar reaction between (DME)NiBr2 and 2-(CN(CH2Ph)(CH)2N)C6H4N═P(Ph2)CH2PPh2 ligand prepared from the imidazolium salt and 1 equiv of LiBun. Tetradentate chelate nickel complex [Ni2-(CN(CH2Ph)(CH)2N)C6H4N═P(Ph2)}2CH]+Cl− was synthesized by transmetalation between (DME)NiCl2 and [Li2-(CN(CH2P

  两个C，N，N -螯合物镍络合物，[镍（Cl）的2-（CN（ME）（CH）2 N）C号6 ħ 4 N = P（PH 2）CH 2比利牛斯}] +我-和[镍（Cl）的2-（CN（镨我）（CH）2 N）C号6 ħ 4 N = P（PH 2）CH 2 P（博士2）= NC 6 H ^ 4 ME-4}] +我-通过（DME）NiCl 2（DME = 1,2-二甲氧基乙烷）与2-（CN（R）（CH）2 N）C 6 H 4反应合成N = P（PH 2）CH 2 Z（R = Me中，Z = 2-比利牛斯; R = PR我，Z = p -MeC 6 ħ 4 N = P（PH 2））配体，其制备在原位由对应咪唑鎓盐与礼部的1个当量的反应ñ。C，N，P螯合物镍络合物[镍（BR）2-（CN（CH 2 PH）（CH）2 N）C号6 ħ 4 N = P（PH 2）CH 2 PPH 2 }] +溴-通过（DME）NiBr