4,4'-bis([trans-bis(trimethylphosphine)chloronickel(II)]methyl)-1,1'-biphenyl | 1244696-79-4

• 英文名称: 4,4'-bis([trans-bis(trimethylphosphine)chloronickel(II)]methyl)-1,1'-biphenyl
• CAS: 1244696-79-4
• 化学式: C₂₆H₄₈Cl₂Ni₂P₄
• 分子量: 672.848
• InChiKey: MVRDYXQFJKZYGZ-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：

  potassium N-(2,6-diisopropylphenyl)-2-(2,6-diisopropylphenylimino)-4-methylpentanamidate 、 4,4'-bis([trans-bis(trimethylphosphine)chloronickel(II)]methyl)-1,1'-biphenyl 以 甲苯 为溶剂， 以73%的产率得到4,4'-bis([N-(2,6-diisopropylphenyl)-2-(2,6-diisopropylphenylimino)-4-methylpentanamidato-κ2-N,O-(trimethylphosphine)nickel(II)]methyl)-1,1'-biphenyl
  参考文献：
  名称：

  Binuclear Initiators for the Telechelic Synthesis of Elastomeric Polyolefins

  摘要：

  Novel binuclear complexes, 4,4'-bis{[N-(2,6-diisopropylphenyl)-2-(2,6-diisopropylphenylimino)-propanamidato-kappa(2)-N,O-(trimethylphosphine)nickel(II)]methyl}-1,1'-biphenyl (2a) and 4,4'-bis{[N-(2,6-diisopropylphenyl)-2-(2,6-diisopropylphenylimino)-4-methylpentamidato-kappa(2)-N,O-(trimethylphosphine)nickel(II)]methyl}-1,1'-biphenyl (2b), were synthesized by linking two nickel centers through a bis(benzyl) fragment. When activated with nickel bis(1,5-cyclooctadiene) (Ni(COD)(2)), 2a and 2b are capable of polymerizing ethylene in a quasi-living fashion, producing polymers with approximately twice the molecular weights relative to those obtained by using a structurally related mononuclear system. In addition, 2b/Ni(COD)(2) was utilized to synthesize a series of pseudo-triblock polyethylene (PE) macroinitiating copolymers, bearing atom-transfer radical polymerization (ATRP) initiators. Pseudo-pentablock copolymers were also prepared by taking advantage of a pressure-pulsing technique, wherein the ethylene pressure was increased from 100 to 500 psi in order to produce semicrystalline ethylene-rich end-blocks. Copolymers with elastomeric properties were synthesized by grafting n-butyl acrylate from the PE macroinitiators via ATRP. Examination using monotonic and step-cyclic stress strain tests demonstrates that the materials exhibit large strains at break (1600-2000%) and excellent elastic recoveries at large strains (similar to 80%). That materials with such desirable properties could not be attained using a mononuclear initiator demonstrates the clear advantage of growing the polymer via a telechelic mechanism.

  DOI：

  10.1021/ja1056938
• 作为产物：
  描述：

  bis(1,5-cyclooctadiene)nickel (0) 、 联苯二氯苄 、 三甲基膦 以 四氢呋喃 为溶剂， 以82%的产率得到4,4'-bis([trans-bis(trimethylphosphine)chloronickel(II)]methyl)-1,1'-biphenyl
  参考文献：
  名称：

  Binuclear Initiators for the Telechelic Synthesis of Elastomeric Polyolefins

  摘要：

  Novel binuclear complexes, 4,4'-bis{[N-(2,6-diisopropylphenyl)-2-(2,6-diisopropylphenylimino)-propanamidato-kappa(2)-N,O-(trimethylphosphine)nickel(II)]methyl}-1,1'-biphenyl (2a) and 4,4'-bis{[N-(2,6-diisopropylphenyl)-2-(2,6-diisopropylphenylimino)-4-methylpentamidato-kappa(2)-N,O-(trimethylphosphine)nickel(II)]methyl}-1,1'-biphenyl (2b), were synthesized by linking two nickel centers through a bis(benzyl) fragment. When activated with nickel bis(1,5-cyclooctadiene) (Ni(COD)(2)), 2a and 2b are capable of polymerizing ethylene in a quasi-living fashion, producing polymers with approximately twice the molecular weights relative to those obtained by using a structurally related mononuclear system. In addition, 2b/Ni(COD)(2) was utilized to synthesize a series of pseudo-triblock polyethylene (PE) macroinitiating copolymers, bearing atom-transfer radical polymerization (ATRP) initiators. Pseudo-pentablock copolymers were also prepared by taking advantage of a pressure-pulsing technique, wherein the ethylene pressure was increased from 100 to 500 psi in order to produce semicrystalline ethylene-rich end-blocks. Copolymers with elastomeric properties were synthesized by grafting n-butyl acrylate from the PE macroinitiators via ATRP. Examination using monotonic and step-cyclic stress strain tests demonstrates that the materials exhibit large strains at break (1600-2000%) and excellent elastic recoveries at large strains (similar to 80%). That materials with such desirable properties could not be attained using a mononuclear initiator demonstrates the clear advantage of growing the polymer via a telechelic mechanism.

  DOI：

  10.1021/ja1056938