(1,5-cyclooctadiene)Pt(C6H4-4-CH3)Cl | 57110-60-8

• 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: (1,5-cyclooctadiene)Pt(C6H4-4-CH3)Cl
• 英文别名: [PtCl(p-tolyl)(η4-COD)]；(COD)Pt(C6H4-4-CH3)Cl；chloroplatinum(1+);(1Z,5Z)-cycloocta-1,5-diene;methylbenzene
• CAS: 57110-60-8
• 化学式: C₁₅H₁₉ClPt
• 分子量: 429.849
• InChiKey: RJVLBUSYZWLJSP-PHFPKPIQSA-M

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：

  (1,5-cyclooctadiene)Pt(C6H4-4-CH3)Cl 、 苯基溴化镁 在 ammonium chloride 作用下， 以 乙醚 为溶剂， 以74%的产率得到(1,5-cyclooctadiene)Pt(C6H4-4-CH3)(C6H5)
  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

• Dynamic Titanium Phosphinoamides as Unique Bidentate Phosphorus Ligands for Platinum
  作者：Hideo Nagashima、Takashi Sue、Takashi Oda、Akira Kanemitsu、Taisuke Matsumoto、Yukihiro Motoyama、Yusuke Sunada

  DOI：10.1021/om0509600

  日期：2006.4.1

  results in formation of titanium phosphinoamides, (Ph2PNR)2TiCl2 [R = tBu (1a), iPr (1b)]. Crystallographic studies show that there are covalent bonds between the titanium and two nitrogen atoms, whereas two phosphorus atoms are coordinated to the metal center intramolecularly. Variable-temperature NMR studies suggest reversible dissociation of the phosphorus moieties from the titanium in solution. The dissociated

  用TiCl 4处理膦膦酰胺锂Ph 2 PN（Li）R [R = t Bu，i Pr]导致形成钛膦酰胺（Ph 2 PNR）2 TiCl 2 [R = t Bu（1a），i（（1b）]。晶体学研究表明，钛和两个氮原子之间存在共价键，而两个磷原子在分子内与金属中心配位。可变温度NMR研究表明，溶液中的磷部分可从钛中发生可逆离解。解离的磷部分被Pt（II）物种有效捕获；的反应1A与（η 4 -COD）氯铂酸2，（η 4 -COD）的Pt（R）（CL）（R = Me中，p -Tol），或[我2的Pt（μ-SMe的2）] 2提供相应的Ti-Pt异双金属配合物。这些配合物的分子结构表明它们具有六元双金属环，其中钛和铂通过两个桥连的膦酰胺配体连接。Pt-Ti距离表明存在Pt→Ti导数键。双金属环的构型是船形的，在船首和船尾有两种金属。然而，从可变温度NMR研究表明，动态构象变化涉及Pt→Ti配位键的断裂和重新形成。