[η2-(t-Bu2P(Br)CH2SiMe2)N(tBu2P(Br)CH2SiMe2)]NiBr2 | 1304126-81-5

• 英文名称: [η2-(t-Bu2P(Br)CH2SiMe2)N(tBu2P(Br)CH2SiMe2)]NiBr2
• 英文别名: [(tBu2P(Br)CH2SiMe2)N(tBu2PCH2SiMe2)]NiBr2
• CAS: 1304126-81-5
• 化学式: C₂₂H₅₂Br₃NNiP₂Si₂
• 分子量: 747.182
• InChiKey: MECAPNNEGHBAFL-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：

  [η2-(t-Bu2PCH2SiMe2)2N]NiBr 、 [η2-(t-Bu2P(Br)CH2SiMe2)N(tBu2P(Br)CH2SiMe2)]NiBr2 以 二氯甲烷-D2 为溶剂， 以0%的产率得到[η2-(t-Bu2PCH2SiMe2)2N]NiBr2
  参考文献：
  名称：

  Evaluating the reducing power of 3-coordinate T-shaped NiI

  摘要：

  The reactivity of (PNP)Ni-I, where PNP = ((Bu2PCH2SiMe2)-Bu-t)(2)N, with oxidants was evaluated. Towards the nitroxyl TEMPO, a 1:1 adduct is formed which was shown to have eta(2)-TEMPO bound through both N and O, with the consequence that one P of the PNP ligand is displaced, leaving the pincer ligand bidentate to Ni-II. DFT calculations show that the bidentate character of TEMPO is due to steric clash between Bu-t and TEMPO ring methyl groups. Reaction of (PNP)Ni with I-2, Br-2, C2Cl6 and even CH2Cl2 all yield (PNP)(NiX)-X-II, but never (PNP)(NiX2)-X-III. Excess Br-2 instead oxidizes one phosphorus, yielding the zwitterion [((BrBu2PCH2SiMe2)-Bu-t)N((SiMe2CH2PBu2)-Bu-t)]NiBr2, whose structure is determined. DFT calculation of the species (PNP)Ni-III(Br)(2) yields reaction thermodynamics which show the reason for its absence, and also shows the low BDE of its Ni-Br bond. (PNP)Ni slowly catalyzes the polymerization of HCCR (R = H or Ph), but gives no detectable conversion to a new alkyne-derived nickel complex. (c) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2010.12.059
• 作为产物：
  描述：

  ((t-Bu2PCH2SiMe2)2N)Ni 、 溴 以 正戊烷 为溶剂， 生成 [η2-(t-Bu2PCH2SiMe2)2N]NiBr 、 [η2-(t-Bu2P(Br)CH2SiMe2)N(tBu2P(Br)CH2SiMe2)]NiBr2
  参考文献：
  名称：

  Evaluating the reducing power of 3-coordinate T-shaped NiI

  摘要：

  The reactivity of (PNP)Ni-I, where PNP = ((Bu2PCH2SiMe2)-Bu-t)(2)N, with oxidants was evaluated. Towards the nitroxyl TEMPO, a 1:1 adduct is formed which was shown to have eta(2)-TEMPO bound through both N and O, with the consequence that one P of the PNP ligand is displaced, leaving the pincer ligand bidentate to Ni-II. DFT calculations show that the bidentate character of TEMPO is due to steric clash between Bu-t and TEMPO ring methyl groups. Reaction of (PNP)Ni with I-2, Br-2, C2Cl6 and even CH2Cl2 all yield (PNP)(NiX)-X-II, but never (PNP)(NiX2)-X-III. Excess Br-2 instead oxidizes one phosphorus, yielding the zwitterion [((BrBu2PCH2SiMe2)-Bu-t)N((SiMe2CH2PBu2)-Bu-t)]NiBr2, whose structure is determined. DFT calculation of the species (PNP)Ni-III(Br)(2) yields reaction thermodynamics which show the reason for its absence, and also shows the low BDE of its Ni-Br bond. (PNP)Ni slowly catalyzes the polymerization of HCCR (R = H or Ph), but gives no detectable conversion to a new alkyne-derived nickel complex. (c) 2011 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2010.12.059