(bis(dicyclohexylphosphino)methane-κ2P)Ni(benzyl)2 | 386298-87-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 金属杂环化合物
• 英文名称: (bis(dicyclohexylphosphino)methane-κ2P)Ni(benzyl)2
• CAS: 386298-87-9
• 化学式: C₃₉H₆₀NiP₂
• 分子量: 649.543
• InChiKey: BYNYOUCGURKNDZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  tetrakis[3,5-bis(trifluoromethyl)phenyl]boric acid bis(diethyl ether) complex 、 (bis(dicyclohexylphosphino)methane-κ2P)Ni(benzyl)2 以 乙醚 为溶剂， 以55%的产率得到[(bis(dicyclohexylphosphino)methane-κ2P)Ni(η3-benzyl)][B(3,5-(CF3)2C6H3)4]
  参考文献：
  名称：

  Crowded Diphosphinomethane Ligands in Catalysis: [(R₂PCH₂PR′₂-κ²P)NiR″]⁺Cations for Ethylene Polymerization without Activators

  摘要：

  The preparation of a series of nickel dichloride complexes with bulky diphosphinomethane chelate ligands R2PCH2PR'(2) is reported. Reaction with the appropriate Grignard reagent leads to the corresponding dimethyl and dibenzyl complexes. Cationic monomethyl and mono-eta(3)-benzyl complexes are generated from these dialkyl complexes by protonation with [H(OEt2)(2)](+)[B(3,5-(CF3)(2)C6H3)(4)](-), while the complex [(dtbpm-K2P)Ni(eta(3)-CH(CH2Ph)Ph](+)[B(3,5-(CF3)(2)C6H3)(4)](-) is obtained from protonation of the Ni(0) olefin complex (dtbpm-kappa P-2)Ni(eta(2)-trans-stilbene). Crystal structures of examples of dichlorides, dimethyl, dibenzyl, cationic methyl, and cationic eta(3)-benzyl complexes are reported. Solutions of the cations polymerize ethylene under mild conditions and without the necessity of an activating agent, to form polyethylene having high molecular weights and low degrees of chain branching. In comparison to the Ni methyl cations, the eta(3)-benzyl cation complexes are more stable and somewhat less active but still very efficient in C2H4 polymerization. The effect on the resulting polyethylene of varying the substituents R, R' on the phosphine ligand has been examined, and a dear trend for longer chain PE with less branching in the presence of more bulky substituents on the diphosphine has been found. Density functional calculations have been used to examine the rapid suprafacial eta(3) to eta(3) haptotropic shift processes of the [(R2PCH2PR'(2))Ni] fragment and the eta(3)-eta(1) change of the coordination mode of the benzyl group required for polymerization in those cations.

  DOI：

  10.1021/om200715w
• 作为产物：
  描述：

  双(二环己基膦)甲烷 以 乙醚 、 乙醇 、 正戊烷 为溶剂， 生成 (bis(dicyclohexylphosphino)methane-κ2P)Ni(benzyl)2
  参考文献：
  名称：

  Crowded Diphosphinomethane Ligands in Catalysis: [(R₂PCH₂PR′₂-κ²P)NiR″]⁺Cations for Ethylene Polymerization without Activators

  摘要：

  The preparation of a series of nickel dichloride complexes with bulky diphosphinomethane chelate ligands R2PCH2PR'(2) is reported. Reaction with the appropriate Grignard reagent leads to the corresponding dimethyl and dibenzyl complexes. Cationic monomethyl and mono-eta(3)-benzyl complexes are generated from these dialkyl complexes by protonation with [H(OEt2)(2)](+)[B(3,5-(CF3)(2)C6H3)(4)](-), while the complex [(dtbpm-K2P)Ni(eta(3)-CH(CH2Ph)Ph](+)[B(3,5-(CF3)(2)C6H3)(4)](-) is obtained from protonation of the Ni(0) olefin complex (dtbpm-kappa P-2)Ni(eta(2)-trans-stilbene). Crystal structures of examples of dichlorides, dimethyl, dibenzyl, cationic methyl, and cationic eta(3)-benzyl complexes are reported. Solutions of the cations polymerize ethylene under mild conditions and without the necessity of an activating agent, to form polyethylene having high molecular weights and low degrees of chain branching. In comparison to the Ni methyl cations, the eta(3)-benzyl cation complexes are more stable and somewhat less active but still very efficient in C2H4 polymerization. The effect on the resulting polyethylene of varying the substituents R, R' on the phosphine ligand has been examined, and a dear trend for longer chain PE with less branching in the presence of more bulky substituents on the diphosphine has been found. Density functional calculations have been used to examine the rapid suprafacial eta(3) to eta(3) haptotropic shift processes of the [(R2PCH2PR'(2))Ni] fragment and the eta(3)-eta(1) change of the coordination mode of the benzyl group required for polymerization in those cations.

  DOI：

  10.1021/om200715w