[sym-([2.1.1]-(2,6)-pyridinophane)Pt(IV)Me2H]B(C6H3(CF3)2)4] | 547695-25-0

• 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: [sym-([2.1.1]-(2,6)-pyridinophane)Pt(IV)Me2H]B(C6H3(CF3)2)4]
• 英文别名: [(η3-[2.1.1]-2,6-pyridinophane)Pt(IV)HMe2]B[3,5-(CF3)2C6H3]4；[PtMe2H(η3-[2.1.1]-(2,6)-pyridinophane)] tetrakis[3,5-bis(trifluoromethyl)phenyl]borate；[PtMe2H(eta.3-[2.1.]-(2,6)-pyridinophane)]BAr4(F)；[unsym-([2.1.1]-(2,6)-pyridinophane)Pt(IV)Me2H]B(C6H3(CF3)2)4]
• CAS: 547695-25-0；717139-15-6
• 化学式: C₂₁H₂₄N₃Pt*C₃₂H₁₂BF₂₄
• 分子量: 1376.74
• InChiKey: HLHFDYZDVHCJNA-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：

  [sym-([2.1.1]-(2,6)-pyridinophane)Pt(IV)Me2H]B(C6H3(CF3)2)4] 在 benzene 作用下， 以 二氯甲烷 为溶剂， 生成 [(η3-[2.1.1]-2,6-pyridinophane)Pt(IV)H(Me)(Ph)]B[3,5-(CF3)2C6H3]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：

  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

文献信息

• [2.1.1]-(2,6)-Pyridinophane(L)-controlled alkane C–H bond cleavage: (L)PtMe2H+ as a precursor to the geometrically “tense” transient (L)PtMe+Electronic supplementary information (ESI) available: complete experimental and characterization data. See http://www.rsc.org/suppdata/nj/b3/b302055j/.
  作者：Andrei N. Vedernikov、John C. Huffman、Kenneth G. Caulton

  DOI：10.1039/b302055j

  日期：2003.3.24

  (η2-L)PtMe2 L=[2.1.1]-(2,6)-pyridinophane} is protonated at Pt to give (η3-L)PtHMe2+, where three pyridine ligands of the macrocycle L bind to Pt in a facial manner. This cation eliminates methane at a rate convenient for trapping of the T-shaped, 14-valence electron (η2-L)PtMe+ (based on DFT geometry optimization) by ethane, propane, n-butane, cyclopentane and cyclohexane to give (η3-L)Pt(olefin)H+

  （η 2 -L）PTME 2 L = [2.1.1] - （2,6）-pyridinophane}在PT的质子化，得到（η 3 -L）PTHMe 2 +，其中3吡啶 配体 的 大循环L以面部方式与PT结合。这阳离子消除甲烷的速率方便T形，14-价电子（η捕集2 -L）PTME + （基于DFT几何优化）通过乙烷， 丙烷， 正丁烷， 环戊烷和环己烷，得到（η 3 -L）的PT（烯烃）H +和CH 4。的（η晶体结构3 -L）的PT（环己烯）H +作为它的BAR F- 4盐被报告。
• 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).