(1,5-cyclooctadiene)Pt(p-dimethylaminophenyl)2 | 90478-97-0

• 英文名称: (1,5-cyclooctadiene)Pt(p-dimethylaminophenyl)2
• 英文别名: (1,5-cyclooctadiene)Pt(C6H4-4-NMe2)2；(COD)Pt(C6H4-4-NMe2)2
• CAS: 90478-97-0
• 化学式: C₂₄H₃₂N₂Pt
• 分子量: 543.611
• InChiKey: NCGQMQMJUDHHNE-KEUNEWJHSA-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：
  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：

  1,1'-双(二苯基膦)二茂铁 、 (1,5-cyclooctadiene)Pt(p-dimethylaminophenyl)2 以 苯 为溶剂， 以95%的产率得到(1,1'-bis(diphenylphosphino)ferrocene)Pt(C6H4-4-NMe2)2
  参考文献：
  名称：

  Distinct Electronic Effects on Reductive Eliminations of Symmetrical and Unsymmetrical Bis-Aryl Platinum Complexes

  摘要：

  Symmetrical bis-aryl platinum complexes (DPPF)Pt(C6H4-4-R)(2) (R = NMe2, OMe, CH3, H, Cl, CF3) and electronically unsymmetrical bis-aryl platinum complexes (DPPF)Pt(C6H4-4-R) (C6H4-4-X) (R = CH3, X = NMe2, OMe, H, Cl, F, CF3; R = OMe, X = NMe2, H, Cl, F, CF3; R = CF3, X = H, Cl, NMe2; and R = NMe2, X = H, Cl) were prepared, and the rates of reductive elimination of these complexes in the presence of excess PPh3 are reported. The platinum complexes reductively eliminated biaryl compounds in quantitative yields with first-order rate constants that were independent of the concentration of PPh3. Plots of Log(k(obs)/k(obs(H))) vs Hammett substituent constants (sigma) of the para substituents R and X showed that the rates of reductive elimination reactions depended on two different electronic properties. The reductive elimination from symmetrical bis-aryl platinum complexes occurred faster from complexes with more electron-donating para substituents R. However, reductive elimination from a series of electronically unsymmetrical bis-aryl complexes was not faster from complexes with the more electron-donating substituents. Instead, reductive elimination was faster from complexes with a larger difference in the electronic properties of the substituents on the two platinum-bound aryl groups. The two electronic effects can complement or cancel each other. Thus, this combination of electronic effects gives rise to complex, but now more interpretable, free energy relationships for reductive elimination.

  DOI：

  10.1021/ja0480365
• 作为产物：
  描述：

  dichloro( 1,5-cyclooctadiene)platinum(ll) 、 4-(N,N-二甲基)苯胺溴化镁 在 ammonium chloride 作用下， 以 乙醚 为溶剂， 以59%的产率得到(1,5-cyclooctadiene)Pt(p-dimethylaminophenyl)2
  参考文献：
  名称：

  Distinct Electronic Effects on Reductive Eliminations of Symmetrical and Unsymmetrical Bis-Aryl Platinum Complexes

  摘要：

  Symmetrical bis-aryl platinum complexes (DPPF)Pt(C6H4-4-R)(2) (R = NMe2, OMe, CH3, H, Cl, CF3) and electronically unsymmetrical bis-aryl platinum complexes (DPPF)Pt(C6H4-4-R) (C6H4-4-X) (R = CH3, X = NMe2, OMe, H, Cl, F, CF3; R = OMe, X = NMe2, H, Cl, F, CF3; R = CF3, X = H, Cl, NMe2; and R = NMe2, X = H, Cl) were prepared, and the rates of reductive elimination of these complexes in the presence of excess PPh3 are reported. The platinum complexes reductively eliminated biaryl compounds in quantitative yields with first-order rate constants that were independent of the concentration of PPh3. Plots of Log(k(obs)/k(obs(H))) vs Hammett substituent constants (sigma) of the para substituents R and X showed that the rates of reductive elimination reactions depended on two different electronic properties. The reductive elimination from symmetrical bis-aryl platinum complexes occurred faster from complexes with more electron-donating para substituents R. However, reductive elimination from a series of electronically unsymmetrical bis-aryl complexes was not faster from complexes with the more electron-donating substituents. Instead, reductive elimination was faster from complexes with a larger difference in the electronic properties of the substituents on the two platinum-bound aryl groups. The two electronic effects can complement or cancel each other. Thus, this combination of electronic effects gives rise to complex, but now more interpretable, free energy relationships for reductive elimination.

  DOI：

  10.1021/ja0480365

文献信息

• Photophysical and electrochemical properties of 1,3-bis(2-pyridylimino)isoindolate platinum(ii) derivatives
  作者：Kenneth Hanson、Luke Roskop、Niral Patel、Laurent Griffe、Peter I. Djurovich、Mark S. Gordon、Mark E. Thompson

  DOI：10.1039/c2dt30354j

  日期：——

  phosphorescence ranging in energy from 594 to 680 nm was observed from the complexes, with quantum efficiencies ranging from 0.01 to 0.05. The efficiency of emission is dictated largely by nonradiative processes since the rate constants for nonradiative deactivation [(1.1–100) × 105 s−1] show greater variation than those for radiative decay [(0.57–4.0) × 04 s−1]. Nonradiative deactivation for compounds

  已经合成并表征了一系列十二个形式为（N ^ N ^ N）PtX的铂（II）配合物，其中N ^ N ^ N是1,3-双（2-吡啶基氨基）异吲哚酸酯配体（BPI）或BPI配体其芳基部分被叔取代-丁基，硝基，烷氧基，碘或氯基，并且X是氯，氟，氰基，乙酸酯，苯基或4-（二甲基氨基）苯基配体。所有络合物在电势下显示至少一个不可逆的氧化和两个可逆的还原波，其电势取决于X和取代的N ^ N ^ N配体两者的位置和给电子或吸电子的性质。从配合物中观察到宽范围的室温磷光，能量范围为594至680 nm，量子效率范围为0.01至0.05。发射效率主要由非辐射过程决定，因为非辐射失活的速率常数[（1.1–100）×10 5 s -1 ]显示出比辐射衰变[（0.57–4.0）×0 4 s -1 ]大的变化率。]。X = Cl的化合物的非辐射失活遵循能隙定律，即，非辐射速率常数随发射能量的降低呈指数增长。激发态的失