Pt(p-CF₃Ph)₂(cod) | 90478-98-1

• 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: Pt(p-CF₃Ph)₂(cod)
• 英文别名: (1,5-cyclooctadiene)Pt(C6H4-4-CF3)2；(COD)Pt(C6H4-4-CF3)2；[Pt(COD)(4-(trifluoromethyl)phenyl)2]；[Pt(C6H4-p-CF3)2(1,5-cyclooctadiene)]；(1Z,5Z)-cycloocta-1,5-diene;platinum(2+);trifluoromethylbenzene
• CAS: 90478-98-1
• 化学式: C₂₂H₂₀F₆Pt
• 分子量: 593.471
• InChiKey: WKHIOCQGJXZSJH-PHFPKPIQSA-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：

  二异丁基膦 、 Pt(p-CF₃Ph)₂(cod) 以 正己烷 为溶剂， 以91%的产率得到cis-[Pt(C6H4-p-CF3)2(PH(i-Bu)2)2]
  参考文献：
  名称：

  Dialkyl- and diaryl-platinum(II) complexes with secondary phosphines: Preparation, structure and thermal reaction giving the metallopolymer

  摘要：

  Alkyl and arylplatinum complexes with 1,5-cyclooctadiene ligand, [PtR2(cod)] (R = Me, Ph, C6H4-p-CF3, C6F5), react with secondary phosphines, PHR'(2) (R' = i-Bu, t-Bu, Ph), to afford the mononuclear platinum complexes, cis-[PtR2(PHR'(2))(2)] (1a: R = Me, R' = i-Bu; 1b: R = Me, R' = t-Bu; 1c: R = Me, R' = Ph; 2a: R = Ph, R' = i-Bu; 2b: R = Ph, R' = t-Bu; 2c: R = R' = Ph; 3a: R= C6H4-p-CF3, R' = i-Bu; 3b: R= C6H4-p-CF3, R' = t-Bu; 3c: R = C6H4-p-CF3, R' = Ph; 4a: R = C6F5, R' = i-Bu; 4c: R = C6F5, R' = Ph) in 81-98% yields. Molecular structures of the complexes except for 1a, 1c and 2a were determined by X-ray crystallography. Complex 1b has a square-planar structure with Pt-C(methyl) bonds of 2.083(8) and 2.109(8) angstrom, while the Pt-C(aryl) bonds of 2b-c, 3a-c, 4a and 4c (2.055(1)-2.073(8) angstrom) are shorter than them. Thermal decomposition of 1b, 2a-c, and 3a-c releases methane, biphenyl or 4,4'-bis(trifluoromethyl)biphenyl as the organic products, which are characterized by NMR spectroscopy. The solid product of the thermal reactions of 2b and 2c were characterized as the metallopolymers formulated as [Pt(PR'(2))(2)](n) (5b: R' = Bu-t; 5c: R' = Ph), based on the solid-state NMR and elemental analyses. (C) 2009 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2009.03.009
• 作为产物：
  描述：

  dichloro( 1,5-cyclooctadiene)platinum(ll) 、 4-三氟甲基苯基溴化镁 在 ammonium chloride 作用下， 以 乙醚 为溶剂， 以69%的产率得到Pt(p-CF₃Ph)₂(cod)
  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

• η²-Coordination and C−H Activation of Electron-Poor Arenes
  作者：Carl N. Iverson、Rene J. Lachicotte、Christian Müller、William D. Jones

  DOI：10.1021/om020459x

  日期：2002.11.1

  at lower temperatures. Thermolysis or photolysis of the arene complexes results in C−H activation and the formation of platinum(II) aryl hydride complexes. The products observed depend on whether the reaction is thermal or photolytic. Reaction with 4,4‘-bis(trifluoromethyl)biphenyl yields two C−H activated products directly. Oxidative addition occurs at the 2 and 3 positions of the biphenyl in a 5:1

  从（dtbpm）Pt（Np）H（dtbpm =双（二叔丁基膦基）甲烷，Np =新戊基）还原性消除新戊烷导致形成高反应性中间体[（dtbpm）Pt 0 ]。该物质与各种电子不足的苯（1,4-双（三氟甲基）苯和1,3,5-三（三氟甲基）苯）和联苯（3,5,4'-三（三氟甲基）联苯和3,5,3' ，5'-四（三氟甲基）联苯），以形成η 2个-arene络合物。X-射线晶体学确认了η 2 η-键接基序。芳烃配合物均显示广泛1室温下的1 H NMR光谱特征在较低温度下会明显锐化。芳烃配合物的热解或光解导致CH活化并形成氢化铂（II）芳基氢化物配合物。观察到的产物取决于反应是热反应还是光解反应。与4,4'-双（三氟甲基）联苯反应可直接产生两个CH活化的产物。氧化加成分别在联苯的2和3位以5：1的比例发生。继续加热混合物会导致第二次CH活化，形成铂环戊烷。
• R/X exchange reactions in cis-[M(R)₂{P(X)(NMeCH₂)₂}₂] (M = Pd, Pt), via a phosphenium intermediate
  作者：Masumi Itazaki、Noriko Tsuchida、Yuka Shigesato、Keiko Takano、Hiroshi Nakazawa

  DOI：10.1039/c6dt02314b

  日期：——

  R/X exchange reactions in cis-[M(R)2P(X)(NMeCH2)2}2] (M = Pd, Pt; R = aryl, alkyl; X = Cl, Br) were achieved for the first time to give cis-[M(X)2P(R)(NMeCH2)2}2]. DFT calculations suggested that the exchange reaction proceeds via a phosphenium intermediate.

  对于顺式-[M（R）2 P（X）（NMeCH 2）2 } 2 ]（M = Pd，Pt; R =芳基，烷基; X = Cl，Br），进行R / X交换反应。第一次给出顺式-[M（X）2 P（R）（NMeCH 2）2 } 2 ]。DFT计算表明交换反应通过via中间体进行。