diphenyl(1,1'-bis(diphenylphosphino)ferrocene)platinum(II) | 209181-55-5

• 英文名称: diphenyl(1,1'-bis(diphenylphosphino)ferrocene)platinum(II)
• 英文别名: [Pt(dppf)(Ph)2]；(DPPF)Pt(C6H5)2；(1,1'-bis(diphenylphosphino)ferrocene)Pt(C6H5)2
• CAS: 209181-55-5
• 化学式: C₄₆H₃₈FeP₂Pt
• 分子量: 903.682
• InChiKey: WZAKREWGQQCMLO-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：

  diphenyl(1,1'-bis(diphenylphosphino)ferrocene)platinum(II) 、 三苯基膦 以 氘代甲苯 为溶剂， 生成 三苯基膦铂 、 [Pt(1,1′-bis(diphenylphosphanyl)ferrocene)₂]
  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
• 作为产物：
  描述：

  1,1'-双(二苯基膦)二茂铁 、 diphenyl(1,5-cyclooctadiene)platinum(II) 以 二氯甲烷 为溶剂， 以97%的产率得到diphenyl(1,1'-bis(diphenylphosphino)ferrocene)platinum(II)
  参考文献：
  名称：

  Cp 2 Fe（PPh 2）2 PtPh 2和Cp 2 Fe（PPh 2）2 PtI 2的合成，单晶X射线结构测定和NMR研究

  摘要：

  二苯基[1,1'-双（二苯基膦基）二茂铁]铂（II），Cp 2 Fe（PPh 2）2 PtPh 2（1）和二碘[1,1'-双（二苯基膦基）二茂铁]铂（II），的Cp 2的Fe（PPH 2）2 PTI 2（2）在几乎定量的产率，允许的Cp合成，具有优异的纯度2的Fe（PPH 2）2与（COD）乍得人道主义保护反应2和（COD）PTI 2（COD = 1,5-环辛二烯）。化合物1和2各种分析和光谱技术，以及单晶X射线衍射都很好地表征了这种技术。两种配合物中的铂似乎都具有扭曲的方形平面几何形状。有趣的是，分别为1（101.2（1）Å）和2（100.6（1）Å）的咬合角（P–Pt–P键角）偏离了理想的90°情况，并且比报道的结构dppfPtCl大2 [dppf ＝ 1，1′-双（二苯基膦基）二茂铁]。对这些化合物进行了详细的NMR研究，包括2D和模拟实验，以实现完整的结构分配。化合物1和2在三斜空间基团P结晶和P与一个=

  DOI：

  10.1016/s0022-328x(97)00691-8

文献信息

• Phosphine and N-heterocyclic carbene ligands on Pt(II) shift selectivity from ethylene hydrophenylation toward benzene vinylation
  作者：Anna M. Brosnahan、Austin Talbot、Bradley A. McKeown、Steven E. Kalman、T. Brent Gunnoe、Daniel H. Ess、Michal Sabat

  DOI：10.1016/j.jorganchem.2015.03.019

  日期：2015.9

  A series of Pt(II) complexes of the type ([(L∼L)Pt(L′)(Ph)][BAr′4] (L∼L = 1,2-bis(dimethylphosphino)ethane, 1,2-bis(diphenylphosphino)ethane, (N-pyrrolyl)2P(CH2)2P(N-pyrrolyl)2, 1,3-bis(diphenylphosphino)propane, 1,1′-bis(diphenylphosphino)ferrocene, (bis-(diphenylphosphino)methyl)methylamine, 8-(diisopropylphosphino)quinoline, 1,1′-methylene-3,3′-di-tert-butylimidazol-2,2′-diylidine); L′ = THF or

  一系列的Pt（II）的类型的复合物（[（L~L）铂（L'）（PH）] [巴' 4 ]（L~L = 1,2-双（二甲基膦基）乙烷，1,2-双（二苯基膦基）乙烷，（ñ吡咯基）2 P（CH 2）2 P（ñ吡咯基）2，1,3-二（二苯基膦基）丙烷，1,1'-双（二苯基膦基）二茂铁，（双-（二苯基膦基）甲基）甲胺，8-（二异丙基膦基）喹啉，1,1'-亚甲基-3,3'-二叔丁基-丁基咪唑-2,2'-二亚甲基）; 已经合成并完全表征了L'= THF或NCMe）。筛选出这些络合物作为乙烯加氢苯基化以产生乙苯的催化剂。所有的配合物对苯乙烯的生产都显示出低催化转化率的选择性。DFT计算已经被用于所述的模型反应[（DMPE）铂（L'）（PH）] [巴' 4 ]（DMPE = 1,2-双（二甲基膦基）乙烷）。结果表明，选择性苯乙烯形成是一个计算ΔΔ的结果ģ ‡ 5千卡在催化循环苯C-H活化步骤，用于与苯乙烯形成乙苯/摩尔。
• The Importance of Ligand Steric Effects on Transmetalation
  作者：Matthew L. Clarke、Mattias Heydt

  DOI：10.1021/om050724p

  日期：2005.12.1

  A very striking phosphine steric effect on the rate of transmetalation of phenyl zinc bromide to platinum complexes has been observed:  most Pt(II) complexes of type [Pt(diphosphine)(Ph)Br] react with PhZnBr rapidly, the slowest reacting complexes being those derived from bis(dicyclohexylphosphino)ethane and bis(di-tert-butylphosphino)xylene.

  已观察到磷化氢对苯基溴化锌向铂络合物的金属转移速率具有非常显着的空间效应：大多数[Pt（diphosphine）（Ph）Br]型Pt（II）络合物与PhZnBr迅速反应，反应最慢的是衍生自双（二环己基膦基）乙烷和双（二叔丁基膦基）二甲苯的那些。