bis(1-(diethylphosphino)-2-(diphenylphosphino)ethane)nickel(0) | 340734-69-2

• 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: bis(1-(diethylphosphino)-2-(diphenylphosphino)ethane)nickel(0)
• 英文别名: [Ni(dedpe)2]
• CAS: 340734-69-2
• 化学式: C₃₆H₄₈NiP₄
• 分子量: 663.362
• InChiKey: FEQKHBNJVHWSEN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.28
• 重原子数：
  41.0
• 可旋转键数：
  8.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  4-methoxyanilinium tetrafluoroborate 、 bis(1-(diethylphosphino)-2-(diphenylphosphino)ethane)nickel(0) 以 四氢呋喃 为溶剂， 以81%的产率得到[HNi(1-(diethylphosphino)-2-(diphenylphosphino)ethane)2](BF4)
  参考文献：
  名称：

  Free-Energy Relationships between the Proton and Hydride Donor Abilities of [HNi(diphosphine)₂]⁺ Complexes and the Half-Wave Potentials of Their Conjugate Bases

  摘要：

  A linear free-energy relationship exists between the half-wave potentials of the (II/I) couples of Ni(diphosphine)(2) complexes and the hydride donor ability (DeltaG(H)(o)(-)) of the corresponding [HNi(diphosphine)(2)](+) complexes. A similar correlation is observed between the half-wave potentials of the (I/O) couples of Ni(diphosphine)(2) complexes and the pK(a) values (or DeltaG(H)(o)(+)) of the corresponding [HNi(diphosphine)(2)](+) complexes. As a result, it is possible to use the potentials of these two couples to predict the free energies of all three Ni-H bond cleavage reactions, DeltaG(H)(o)(+), DeltaG(H)(o)(.), and DeltaG(H)(o)(-), for this class of nickel complexes. The molecular structures of Ni(Et2PCH2CH2PPh2)(2) and Ni(Ph2PCHCHPPh2)(2) were determined by single-crystal Ii-ray diffraction studies.

  DOI：

  10.1021/om0100582
• 作为产物：
  描述：

  [HNi(1-(diethylphosphino)-2-(diphenylphosphino)ethane)2](BF4) 在 (C₂H₅)3N 作用下， 以 乙腈 为溶剂， 生成 bis(1-(diethylphosphino)-2-(diphenylphosphino)ethane)nickel(0)
  参考文献：
  名称：

  Free-Energy Relationships between the Proton and Hydride Donor Abilities of [HNi(diphosphine)₂]⁺ Complexes and the Half-Wave Potentials of Their Conjugate Bases

  摘要：

  A linear free-energy relationship exists between the half-wave potentials of the (II/I) couples of Ni(diphosphine)(2) complexes and the hydride donor ability (DeltaG(H)(o)(-)) of the corresponding [HNi(diphosphine)(2)](+) complexes. A similar correlation is observed between the half-wave potentials of the (I/O) couples of Ni(diphosphine)(2) complexes and the pK(a) values (or DeltaG(H)(o)(+)) of the corresponding [HNi(diphosphine)(2)](+) complexes. As a result, it is possible to use the potentials of these two couples to predict the free energies of all three Ni-H bond cleavage reactions, DeltaG(H)(o)(+), DeltaG(H)(o)(.), and DeltaG(H)(o)(-), for this class of nickel complexes. The molecular structures of Ni(Et2PCH2CH2PPh2)(2) and Ni(Ph2PCHCHPPh2)(2) were determined by single-crystal Ii-ray diffraction studies.

  DOI：

  10.1021/om0100582

文献信息

• Reduction of oxygen catalyzed by nickel diphosphine complexes with positioned pendant amines
  作者：Jenny Y. Yang、R. Morris Bullock、William G. Dougherty、W. Scott Kassel、Brendan Twamley、Daniel L. DuBois、M. Rakowski DuBois

  DOI：10.1039/b921245k

  日期：——

  Nickel(II) bis(diphosphine) complexes that contain positioned bases in the second coordination sphere have been found to catalyze the reduction of O2 with H2 to selectively form water. The complexes also serve as electrocatalysts for the reduction of O2 with the addition of a weak acid. In contrast, a closely related nickel diphosphine complex without the positioned bases is catalytically inactive

  镍（II）双（二膦）已发现在第二配位域中包含定位碱基的配合物可催化O 2与H 2的还原反应，从而选择性地形成水。配合物还可以用作电催化剂，通过添加弱酸来还原O 2。相反，密切相关二膦镍没有定位碱基的配合物对于O 2还原没有催化活性。这些结果表明，用于还原O 2的合成催化剂中的侧基可以起到酶中质子中继的类似作用，并且在设计用于多电子和多质子反应的催化剂时应考虑使用此类中继。