(bis(dicyclohexylphosphino)methane-κ2P)NiCl2 | 284671-07-4

• 英文名称: (bis(dicyclohexylphosphino)methane-κ2P)NiCl2
• CAS: 284671-07-4
• 化学式: C₂₅H₄₆Cl₂NiP₂
• 分子量: 538.184
• InChiKey: SQYIAWZRDSKRRH-UHFFFAOYSA-L

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：

  (bis(dicyclohexylphosphino)methane-κ2P)NiCl2 、 苄基氯化镁 以 乙醚 、 正戊烷 为溶剂， 以73%的产率得到(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
• 作为产物：
  描述：

  双(二环己基膦)甲烷 、 nickel dichloride 以 乙醇 为溶剂， 以70%的产率得到(bis(dicyclohexylphosphino)methane-κ2P)NiCl2
  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

文献信息

• Metal−Metal Interactions in Dinuclear d⁸ Metal Cyanide Complexes Supported by Phosphine Ligands. Spectroscopic Properties and ab Initio Calculations of [M₂(<i>μ</i>-diphosphine)₂(CN)₄] and <i>trans</i>-[M(phosphine)₂(CN)₂] (M = Pt, Ni)
  作者：Bao-Hui Xia、Chi-Ming Che、David Lee Phillips、King-Hung Leung、Kung-Kai Cheung

  DOI：10.1021/ic020077j

  日期：2002.7.1

  Structural, spectroscopic properties on the dinuclear [M(2)(dcpm)(2)(CN)(4)] (M = Pt, 1a; Ni, 2a, dcpm = bis(dicyclohexylphosphino)methane) and [M(2)(dmpm)(2)(CN)(4)] (M = Pt, 1b; Ni, 2b, dmpm = bis(dimethylphosphino)methane) and the mononuclear trans-[M(PCy(3))(2)(CN)(2)] (M = Pt, 3; Ni, 4, PCy(3) = tricyclohexylphosphine) and theoretical investigations on the corresponding model compounds are described

  双核[M（2）（dcpm）（2）（CN）（4）]的结构，光谱性质（M = Pt，1a； Ni，2a，dcpm =双（二环己基膦基）甲烷）和[M（2） （dmpm）（2）（CN）（4）]（M = Pt，1b; Ni，2b，dmpm =双（二甲基膦基）甲烷）和单核反-[M（PCy（3））（2）（CN ）（2）]（M = Pt，3; Ni，4，PCy（3）=三环己基膦）以及对相应模型化合物的理论研究进行了描述。X射线结构分析显示，对于1a / 1b和2a / 2b，Pt.Pt和Ni.Ni距离分别为3.0565（4）/3.189（1）A和2.957（1）/3.209（8）A. 1a和328 nm（epsilon 2.43 x 10（4）dm）在337 nm（epsilon 2.41 x 10（4）dm（3）mol（-）（1）cm（-）（1））的UV-vis吸收带（3）CH（2）Cl（2）中1b的m