(2,6-C6H3(CH2P(CF3)2)2)Pt(η2-ethylene)B(C6F5)4 | 1120346-79-3

• 英文名称: (2,6-C6H3(CH2P(CF3)2)2)Pt(η2-ethylene)B(C6F5)4
• CAS: 1120346-79-3
• 化学式: C₁₄H₁₁F₁₂P₂Pt*C₂₄BF₂₀
• 分子量: 1343.29
• InChiKey: YXFMPRGFNJDRKQ-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：

  丁烯 、 (2,6-C6H3(CH2P(CF3)2)2)Pt(η2-ethylene)B(C6F5)4 以 further solvent(s) 为溶剂， 生成 (2,6-C6H3(CH2P(CF3)2)2)Pt(η2-1-butene)B(C6F5)4
  参考文献：
  名称：

  Acceptor Pincer Coordination Chemistry of Platinum: Reactivity Properties of (^CF₃PCP)Pt(L)⁺ (L = NC₅F₅, C₂H₄)

  摘要：

  Synthetic strategies toward the synthesis of electron-poor pincer complexes ((PCP)-P-CF3)PtH and ((PCP)-P-CF3)Pt(eta(2)-H-2)(+) are described. Metathesis of ((PCP)-P-CF3)PtCl with hydride reagents does not lead to ((PCP)-P-CF3)PtH; ((PCP)-P-CF3)PtCl with KH in tetrahydrofuran (THF) afforded an unusual metallated bimetallic pincer product ((PCP)-P-CF3)Pt[kappa(1)-C,kappa P3-,C,P-2,6-(CHP(CF3)(2))(CH2P(CF3)(2))-C6H3]PtCl, which has been structurally characterized. Chloride abstraction from ((PCP)-P-CF3)PtCl or protonolysis of ((PCP)-P-CF3)PtMe in the presence of H-2 gives the structurally characterized hydride-bridged dimer {((PCP)-P-CF3)Pt}(2)(mu-H)(+). In the presence of trapping ligands H2O, C2H4, or pentafluoropyridine, the corresponding complexes ((PCP)-P-CF3)Pt(L)(+) (L = H2O, C2H4, NC5F5) are cleanly produced and have been structurally characterized. The C2H4 and NC5F5 adducts may be alternatively prepared by methide abstraction from (CF3PCP)PtMe with Ph3C+B(C6F5)(4)(-) in the presence of trapping ligand. Evidence for the transient formation of ((PCP)-P-CF3)PtH from treatment of ((PCP)-P-CF3)PtCl or ((PCP)-P-CF3)Pt(NC5F5)(+) with Et3Si+B(C6F5)(4)(-) is presented. ((PCP)-P-CF3)Pt(C2H4)(+) serves as a catalyst for ethylene hydrogenation (0.30 turnovers h(-1), 70 degrees C) and hydrosilation with Et3SiH (460 turnovers h(-1), RT) and Cl3SiH (5 turnovers h(-1), RT). At elevated temperatures, ((PCP)-P-CF3)Pt(C2H4)(+) also exhibits limited ethylene dimerization activity (0.07 turnovers h(-1), 155 degrees C and 1-butene isomerization (0.9 turnovers h(-1), 80 degrees C).

  DOI：

  10.1021/om8008876
• 作为产物：
  描述：

  乙烯 、 (mesitylenium)B(C6F5)4 、 (2,6-C6H3(CH2P(CF3)2)2)PtMe 以 further solvent(s) 为溶剂， 以53%的产率得到(2,6-C6H3(CH2P(CF3)2)2)Pt(η2-ethylene)B(C6F5)4
  参考文献：
  名称：

  Acceptor Pincer Coordination Chemistry of Platinum: Reactivity Properties of (^CF₃PCP)Pt(L)⁺ (L = NC₅F₅, C₂H₄)

  摘要：

  Synthetic strategies toward the synthesis of electron-poor pincer complexes ((PCP)-P-CF3)PtH and ((PCP)-P-CF3)Pt(eta(2)-H-2)(+) are described. Metathesis of ((PCP)-P-CF3)PtCl with hydride reagents does not lead to ((PCP)-P-CF3)PtH; ((PCP)-P-CF3)PtCl with KH in tetrahydrofuran (THF) afforded an unusual metallated bimetallic pincer product ((PCP)-P-CF3)Pt[kappa(1)-C,kappa P3-,C,P-2,6-(CHP(CF3)(2))(CH2P(CF3)(2))-C6H3]PtCl, which has been structurally characterized. Chloride abstraction from ((PCP)-P-CF3)PtCl or protonolysis of ((PCP)-P-CF3)PtMe in the presence of H-2 gives the structurally characterized hydride-bridged dimer {((PCP)-P-CF3)Pt}(2)(mu-H)(+). In the presence of trapping ligands H2O, C2H4, or pentafluoropyridine, the corresponding complexes ((PCP)-P-CF3)Pt(L)(+) (L = H2O, C2H4, NC5F5) are cleanly produced and have been structurally characterized. The C2H4 and NC5F5 adducts may be alternatively prepared by methide abstraction from (CF3PCP)PtMe with Ph3C+B(C6F5)(4)(-) in the presence of trapping ligand. Evidence for the transient formation of ((PCP)-P-CF3)PtH from treatment of ((PCP)-P-CF3)PtCl or ((PCP)-P-CF3)Pt(NC5F5)(+) with Et3Si+B(C6F5)(4)(-) is presented. ((PCP)-P-CF3)Pt(C2H4)(+) serves as a catalyst for ethylene hydrogenation (0.30 turnovers h(-1), 70 degrees C) and hydrosilation with Et3SiH (460 turnovers h(-1), RT) and Cl3SiH (5 turnovers h(-1), RT). At elevated temperatures, ((PCP)-P-CF3)Pt(C2H4)(+) also exhibits limited ethylene dimerization activity (0.07 turnovers h(-1), 155 degrees C and 1-butene isomerization (0.9 turnovers h(-1), 80 degrees C).

  DOI：

  10.1021/om8008876