Pt([2.1.1]-(2,6)-pyridinophane)Me2 | 501943-24-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 三唑并吡啶类
• 英文名称: Pt([2.1.1]-(2,6)-pyridinophane)Me2
• 英文别名: ([2.1.1]-(2,6)-pyridinophane)Pt(II)Me2
• CAS: 501943-24-4
• 化学式: C₂₁H₂₃N₃Pt
• 分子量: 512.514
• InChiKey: AFZOZYQRDVPPJO-UHFFFAOYSA-N

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：

  hydrogen tetrakis(3,5-bis(trifluoromethyl)phenyl)borate 、 Pt([2.1.1]-(2,6)-pyridinophane)Me2 以 not given 为溶剂， 生成 [sym-([2.1.1]-(2,6)-pyridinophane)Pt(IV)Me2H]B(C6H3(CF3)2)4]
  参考文献：
  名称：

  N–PtIV–H/N–H⋯PtII intramolecular redox equilibrium in a product of H–C(sp2) cleavage and unusual alkane/arene C–H bond selectivity of ([2.1.1]pyridinophane)PtII(CH3)+Electronic supplementary information (ESI) available: experimental details. See http://www.rsc.org/suppdata/cc/b2/b207797n/

  摘要：

  T型14价电子（η²-L）PtMe+（基于DFT几何优化，L = [2.1.1]-2,6-吡啶膦）与苯反应生成（η³-L）PtIV(Ph)₂H+和甲烷；后者阳离子与N-质子化的PtII互变异构体（η²-L-H）Pt(Ph)₂+处于热平衡，这些络合物与乙烷或环戊烷反应生成苯和（L）PtH(烯)+。

  DOI：

  10.1039/b207797n
• 作为产物：
  描述：

  [PtMe₂(SMe₂)]₂ 、 [2.1.1]-(2,6)-pyridinophane 以 not given 为溶剂， 生成 Pt([2.1.1]-(2,6)-pyridinophane)Me2
  参考文献：
  名称：

  N–PtIV–H/N–H⋯PtII intramolecular redox equilibrium in a product of H–C(sp2) cleavage and unusual alkane/arene C–H bond selectivity of ([2.1.1]pyridinophane)PtII(CH3)+Electronic supplementary information (ESI) available: experimental details. See http://www.rsc.org/suppdata/cc/b2/b207797n/

  摘要：

  T型14价电子（η²-L）PtMe+（基于DFT几何优化，L = [2.1.1]-2,6-吡啶膦）与苯反应生成（η³-L）PtIV(Ph)₂H+和甲烷；后者阳离子与N-质子化的PtII互变异构体（η²-L-H）Pt(Ph)₂+处于热平衡，这些络合物与乙烷或环戊烷反应生成苯和（L）PtH(烯)+。

  DOI：

  10.1039/b207797n

文献信息

• [<i>n</i>.1.1]-(2,6)-Pyridinophanes:  A New Ligand Type Imposing Unusual Metal Coordination Geometries
  作者：Andrei N. Vedernikov、John C. Huffman、Kenneth G. Caulton

  DOI：10.1021/ic020430l

  日期：2002.12.1

  A series of new ligands with three pyridines linked into a macrocycle by various CH(2), CMe(2), and CH(2)CH(2) groups at all sites ortho to the pyridine nitrogen have been synthesized and attached to PdCl(2) or PtMe(2). The ligands bind to them through only two nitrogens, and the third pyridine is constrained in close proximity to the planar complex with a filled d(z)2 orbital. Rapid reversible migration

  已合成了一系列具有三个吡啶的新配体，这些吡啶通过在吡啶氮的所有位置上的所有CH（2），CMe（2）和CH（2）CH（2）基团连接到大环中并与PdCl（ 2）或PtMe（2）。配体仅通过两个氮原子与它们结合，并且第三个吡啶被紧密填充的平面d（z）2轨道所约束。PdCl（2）或PtMe（2）向未使用的吡啶氮的快速可逆迁移在CH（2）桥接大环的情况下在20摄氏度下观察到，而在CMe（2）-情况下则不会发生-桥式类似物，并已通过NMR和计算技术确定了这种通量的机理。
• Hydrocarbyl Ligand “Tuning” of the Pt^II/IV Redox Potential
  作者：Andrei N. Vedernikov、Maren Pink、Kenneth G. Caulton

  DOI：10.1021/ic034731m

  日期：2004.6.1

  The potentially tridentate macrocycle [2.1.1]-(2,6)-pyridinophane (L) enables the transient LPtII(CH3)(+) to cleave the C-H bond of two molecules of C6F5H. The resulting product has two aryl groups on Pt but, in contrast to nonfluorinated analogue, varies in its location of the cleaved H, as is evident from the two products (HL+)(PtR2)-R-II and (eta(3)-L)-(PtH)-H-IV(R)(2)(+). At equilibrium, the related example where R = CH3 is purely the Pt-IV redox isomer, which with R = C6H5 shows detectable populations of both isomers, and with R = C6F5 is purely the pyridine-protonated (HL+)Pt-II redox isomer. All species show a hydrogen bond from the pyridinium proton to Pt-II. Consistent with the idea that electron-withdrawing R makes platinum(II) more resistant to oxidation (i.e., a proton on Pt), and thus less Bronsted basic, the (1)J(PtH) coupling constant falls in the series R = Me (90 Hz), R = C6H5 (86 Hz), and R = C6F5 (63 Hz).