[Ni(η2-CH2C6H4Me)(PhP(C2H4PPh2)2)]BPh4 | 852356-16-2

• 英文名称: [Ni(η2-CH2C6H4Me)(PhP(C2H4PPh2)2)]BPh4
• CAS: 852356-16-2
• 化学式: C₂₄H₂₀B*C₄₂H₄₂NiP₃
• 分子量: 1017.64
• InChiKey: DFPNIRQBYAZYLN-UHFFFAOYSA-N

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：
  None

反应信息

• 作为反应物：
  描述：

  盐酸 、 [Ni(η2-CH2C6H4Me)(PhP(C2H4PPh2)2)]BPh4 以 乙腈 为溶剂， 生成 [bis(2-diphenylphosphinoethyl)phenylphosphine]chloronickel(II) tetraphenylborate
  参考文献：
  名称：

  Synthesis of [Ni(η2-CH2C6H4R-4){PPh(CH2CH2PPh2)2}]+ (R=H, Me or MeO) and protonation reactions with HCl

  摘要：

  The complexes [Ni(eta(2)-CH2C6H4R-4)(triphos)]BPh4 {R = H, Me or MeO; triphos = PhP(CH2CH2PPh2)(2)} have been prepared and characterised by spectroscopy and X-ray crystallography. In all cases the coordination geometry of the nickel is best described as square-planar with an eta(2)-benzyl ligand occupying one of the positions. The orientation of the eta(2)-benzyl ligand is dictated by the steric restrictions imposed by the phenyl groups on the triphos ligand, so that the phenyl group on the unique secondary phosphorus and the aromatic group of the benzyl ligand (which are trans to one another) are oriented in the same direction. [Ni(eta(2)-CH2C6H4R-4)(triphos)](+) react with an excess of anhydrous HCl in MeCN to form [NiCl(triphos)](+) (characterised as the [BPh4](-) salt by X-ray crystallography) and the corresponding substituted toluene. The kinetics of the reaction of all [Ni(eta(2)-CH2C6H4R-4)(triphos)](+) and HCl in the presence of Cl- have been determined using stopped-flow spectrophotometry. All reactions exhibit a first-order dependence on the concentration of complex and a first-order dependence on the ratio [HCl]/[Cl-]. Varying the 4-R-substituent on the benzyl ligand shows that electron-withdrawing substituents facilitate the rate of the reaction. It is proposed that the mechanism involves initial rapid protonation at the nickel to form [NiH(eta(2)-CH2C6H4R-4)(triphoS)](2+), followed by intramolecular proton migration from nickel to carbon to yield the products. (c) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2005.01.034
• 作为产物：
  描述：

  [bis(2-diphenylphosphinoethyl)phenylphosphine]chloronickel(II) tetraphenylborate 、 4-甲基苄基氯化镁 以 四氢呋喃 为溶剂， 生成 [Ni(η2-CH2C6H4Me)(PhP(C2H4PPh2)2)]BPh4
  参考文献：
  名称：

  Synthesis of [Ni(η2-CH2C6H4R-4){PPh(CH2CH2PPh2)2}]+ (R=H, Me or MeO) and protonation reactions with HCl

  摘要：

  The complexes [Ni(eta(2)-CH2C6H4R-4)(triphos)]BPh4 {R = H, Me or MeO; triphos = PhP(CH2CH2PPh2)(2)} have been prepared and characterised by spectroscopy and X-ray crystallography. In all cases the coordination geometry of the nickel is best described as square-planar with an eta(2)-benzyl ligand occupying one of the positions. The orientation of the eta(2)-benzyl ligand is dictated by the steric restrictions imposed by the phenyl groups on the triphos ligand, so that the phenyl group on the unique secondary phosphorus and the aromatic group of the benzyl ligand (which are trans to one another) are oriented in the same direction. [Ni(eta(2)-CH2C6H4R-4)(triphos)](+) react with an excess of anhydrous HCl in MeCN to form [NiCl(triphos)](+) (characterised as the [BPh4](-) salt by X-ray crystallography) and the corresponding substituted toluene. The kinetics of the reaction of all [Ni(eta(2)-CH2C6H4R-4)(triphos)](+) and HCl in the presence of Cl- have been determined using stopped-flow spectrophotometry. All reactions exhibit a first-order dependence on the concentration of complex and a first-order dependence on the ratio [HCl]/[Cl-]. Varying the 4-R-substituent on the benzyl ligand shows that electron-withdrawing substituents facilitate the rate of the reaction. It is proposed that the mechanism involves initial rapid protonation at the nickel to form [NiH(eta(2)-CH2C6H4R-4)(triphoS)](2+), followed by intramolecular proton migration from nickel to carbon to yield the products. (c) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2005.01.034