[Pt(PEt3)2((4-bromophenyl)-pyridin-4-yl-diazene)] | 950588-87-1

• 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(PEt3)2((4-bromophenyl)-pyridin-4-yl-diazene)]
• CAS: 950588-87-1
• 化学式: C₂₃H₃₈BrN₃P₂Pt
• 分子量: 693.506
• InChiKey: KRBAYHKLXLAVNM-RBIFHYOVSA-N

反应信息

• 作为反应物：
  描述：

  [Pt(PEt3)2((4-bromophenyl)-pyridin-4-yl-diazene)] 在 C₆H₅Br 作用下， 以 四氢呋喃 为溶剂， 生成 [Pt(PEt3)2Br(phenyl-pyridin-4-yl-diazene(-1H))]
  参考文献：
  名称：

  From Azobenzene Coordination to Aryl−Halide Bond Activation by Platinum

  摘要：

  This contribution describes the reactivity of Pt(PEt3)(4) with (4-bromo-phenyl)-pyridin-4-yl-diazene. eta(2)-Coordination of Pt(PEt3)(2) to the NN moiety is kinetically preferable and followed by an aryl-halide bond activation process. This quantitative transformation proceeds under mild reaction conditions in solution and in the solid state. Mechanistic studies in solution indicate that the metal insertion into the aryl-halide bond is the rate-determining step. The reaction obeys first-order kinetics in the eta(2)-coordination complex with Delta G(298K) = 24.6 +/- 1.6 kcal/mol, Delta H = 26.5 +/- 1.6 kcal/mol, and Delta S = 6.6 +/- 5.0 eu. No effect on the reaction progress and NMR line shape has been observed in the presence of excess PEt3. However, competition experiments with the eta(2)-coordination complex and PhBr reveal that the product ratio can be altered by the presence of PEt3, indicating that the two aryl-halide bond activation processes proceed via different mechanistic pathways. Numerical analysis of a series of competition experiments fits a reaction scheme involving a unimolecular transformation from the eta(2)-coordination complex to the product of aryl-halide oxidative addition. This "ring-walking" process is kinetically accessible as shown by density functional theory (DFT) calculations at the PCM:PBE0/SDB-cc-pVDZ/PBE0/SDD level of theory.

  DOI：

  10.1021/om700519v