NiBr₃(dppey) | 64771-39-7

• 英文名称: NiBr₃(dppey)
• 英文别名: NiBr₃(cis-bis(diphenylphosphino)ethylene)
• CAS: 64771-39-7
• 化学式: C₂₆H₂₂Br₃NiP₂
• 分子量: 694.81
• InChiKey: VHCVKFICSUFBPF-BMKZIQKJSA-K

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：

  NiBr₃(dppey) 以 二氯甲烷 为溶剂， 生成 {nickel(II)(1,2-bis(diphenylphosphino)ethylene)Br2}
  参考文献：
  名称：

  由二级配位球实现的单体镍（III）配合物的卤素光消除

  摘要：

  Endothermic halogen elimination reactions, in which molecular halogen photoproducts are generated in the absence of chemical traps, are rare. Inspired by the proclivity of mononuclear Ni(III) complexes to participate in challenging bond-forming reactions in organometallic chemistry, we targeted Ni(III) trihalide complexes as platforms to explore halogen photoelimination. A suite of Ni(III) trihalide complexes supported by bidentate phosphine ligands has been synthesized and characterized. Multinuclear NMR, EPR, and electronic absorption spectroscopies, as well as single-crystal X-ray diffraction, have been utilized to characterize this suite of complexes as distorted square pyramidal, S = 1/2 mononuclear Ni(III) complexes. All complexes participate in clean halogen photoelimination in solution and in the solid state. Evolved halogen has been characterized by mass spectrometry and quantified chemically. Energy storage via halogen elimination was established by solution-phase calorimetry measurements; in all cases, halogen elimination is substantially endothermic. Time-resolved photochemical experiments have revealed a relatively long-lived photointermediate, which we assign to be a Ni(II) complex in which the photoextruded chlorine radical interacts with a ligand-based aryl group. Computational studies suggest that the observed intermediate arises from a dissociative LMCT excited state. The participation of secondary coordination sphere interactions to suppress back-reactions is an attractive design element in the development of energy-storing halogen photoelimination involving first-row transition metal complexes.

  DOI：

  10.1021/acs.organomet.5b00568
• 作为产物：
  描述：

  {nickel(II)(1,2-bis(diphenylphosphino)ethylene)Br2} 在 bromine 作用下， 以 四氯化碳 为溶剂， 以>99的产率得到NiBr₃(dppey)
  参考文献：
  名称：

  Gray, Leslie R.; Higgins, Simon J.; Levason, William, Journal of the Chemical Society, Dalton Transactions, 1984, p. 459 - 468

  摘要：

  DOI：