{Cp(CO)2W(μ-PPh2)(μ-H)Pt(PPh3)2}BF4 | 137916-12-2

• 英文名称: {Cp(CO)2W(μ-PPh2)(μ-H)Pt(PPh3)2}BF4
• CAS: 137916-12-2
• 化学式: BF₄*C₅₅H₄₆O₂P₃PtW
• 分子量: 1297.62
• InChiKey: IGUKXSPSIMKTAE-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  在 HBF₄*Et₂O 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 以60.9%的产率得到{Cp(CO)2W(μ-PPh2)(μ-H)Pt(PPh3)2}BF4
  参考文献：
  名称：

  Braunstein, Pierre; De Jesús, Ernesto; Tiripicchio, Antonio, Inorganic Chemistry, 1992, vol. 31, # 3, p. 411 - 418

  摘要：

  DOI：

文献信息

• Bridge vs. terminal protonation of isostructural Mo–Pt and W–Pt heterobimetallic compounds
  作者：John Powell、Jeffery F. Sawyer、Stuart J. Smith

  DOI：10.1039/c39850001312

  日期：——

  Protonation of the complexes cp(OC)2[graphic omitted](CO)(PPh3)(cp = cyclopentadienyl) exhibits an M-dependent site selectivity, with protonation occurring at the metal–metal bond for M = Mo to give [cp(OC)2Mo(µ-PPh2)(µ-H)-Pt(CO)PPh3]+ whilst for M = W protonation occurs directly at he tungsten to give a terminal hydrido cation [cp-(OC)2H[graphic omitted](CO)PPh3]+.

  配合物cp（OC）2的质子化[图示省略]（CO）（PPh 3）（cp =环戊二烯基）表现出M依赖的位点选择性，质子化发生在金属-金属键上，M = Mo产生[cp （OC）2 Mo（µ-PPh 2）（µ-H）-Pt（CO）PPh 3 ] +，而对于M = W，质子化直接在钨上发生，从而产生末端氢化阳离子[cp-（OC）2 H [省略的图示]（CO）PPh 3 ] +。
• Synthesis and site-selective protonation of MoPt and WPt bimetallic complexes
  作者：John Powell、Jeffery F. Sawyer、Stuart J. Smith

  DOI：10.1039/dt9920002793

  日期：——

  The reaction of [M(cp)(CO)3(PPh2H)]PH6 1 (M = Mo or W, cp = eta-C5H5) with [Pt(C2H4)(PPh3)2] proceeds rapidly with a 1 : 2 (M : Pt) stoichiometry to give [(OC)2(cp)M(mu-PPh2)Pt(CO)(PPh3)] 4 and [PtH(PPh3)3]PF6 5. However, using an initial 1 : 1 stoichiometry the final product is [(OC)2(cp)M(mu-H)-(mu-PPh2)Pt(PPh3)2]PF6 8. The mechanisms of these reactions are shown to involve deprotonation of 1 to give [(OC)3M(cp)(PPh2)] 2 followed by reaction of the latter with [Pt(C2H4)(PPh3)2] and subsequent transfer of CO from M to Pt to give 4. Protonation of 4 with HBF4 is metal (M) dependent and proceeds to give [(OC)2(cp)Mo(mu-H)(mu-PPh2)Pt(CO)(PPh3)]BF4 12a with M = Mo but for M = W the major product is [(OC)2H(cp)W(mu-PPh2) Pt(CO)(PPh3)] BF4 13b. Variable-temperature H-1 NMR studies show that the terminal hydride cation of 13b is rapidly equilibrating with a small amount of the hydride-bridged isomeric cation [(OC)2(cp)W(mu-H)(mu-PPh2)Pt(CO)(PPh3)]+. Complex 4 reacts with PPh3 (60-degrees-C) and 1,2-bis-(diphenylphosphino)ethane (dppe) at 20-degrees-C to give [(OC)2(cp)M(mu-PPh2)Pt(PPh3)2] 9 and [OC2(cp)-M(mu-PPh2)Pt(dppe)] 10. On bubbling CO through a solution of 9 (20-degrees-C) complex 4 is rapidly regenerated. Reaction of 4 with HCl gives [(OC)2(cp)M(mu-H)(mu-PPh2)PtCl(PPh3)] 15. The molecular structure of [(OC)2(cp)W(mu-PPh2)Pt(CO)(PPh3)] 4b has been determined by single-crystal X-ray diffraction.