{nickel(II)(1,2-bis(diphenylphosphino)ethylene)Br2} | 106564-79-8

• 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: {nickel(II)(1,2-bis(diphenylphosphino)ethylene)Br2}
• 英文别名: NiBr₂(dppey)；NiBr₂(cis-bis(diphenylphosphino)ethylene)
• CAS: 106564-79-8；106564-80-1；23467-50-7；52564-36-0
• 化学式: C₂₆H₂₂Br₂NiP₂
• 分子量: 614.906
• InChiKey: RCGNSAHAJGIIFT-FAIYXUOWSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  7.41
• 重原子数：
  31.0
• 可旋转键数：
  4.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  {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：
• 作为产物：
  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

文献信息

• Trap-Free Halogen Photoelimination from Mononuclear Ni(III) Complexes
  作者：Seung Jun Hwang、David C. Powers、Andrew G. Maher、Bryce L. Anderson、Ryan G. Hadt、Shao-Liang Zheng、Yu-Sheng Chen、Daniel G. Nocera

  DOI：10.1021/jacs.5b03192

  日期：2015.5.27

  Halogen photoelimination reactions constitute the oxidative half-reaction of closed HX-splitting energy storage cycles. Here, we report high-yielding, endothermic Cl2 photoelimination chemistry from mononuclear Ni(III) complexes. On the basis of time-resolved spectroscopy and steady-state photocrystallography experiments, a mechanism involving ligand-assisted halogen elimination is proposed. Employing

  卤素光消除反应构成闭合的 HX 分裂能量存储循环的氧化半反应。在这里，我们报告了单核 Ni(III) 配合物的高产、吸热 Cl2 光消除化学。在时间分辨光谱和稳态光晶体学实验的基础上，提出了一种涉及配体辅助卤素消除的机制。采用辅助配体促进消除提供了一种策略，可以规避 3d 金属配合物固有的短寿命激发态，以激活具有热力学挑战性的键。
• Avetikyan, G. B.; Naslednikova, G. I.; Kukushkin, Yu. N., Russian Journal of Inorganic Chemistry, 1987, vol. 32, p. 1805 - 1805
  作者：Avetikyan, G. B.、Naslednikova, G. I.、Kukushkin, Yu. N.

  DOI：——

  日期：——