[(1,1',2,2'-bisdiphenylphosphinoethane)Pt(CF3)(OH)] | 72953-78-7

• 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: [(1,1',2,2'-bisdiphenylphosphinoethane)Pt(CF3)(OH)]
• 英文别名: (1,2-bis(diphenylphosphino)ethane)Pt(CF3)OH；(1,2-bis(diphenylphosphino)ethane)Pt(CF3)(OH)
• CAS: 72953-78-7
• 化学式: C₂₇H₂₅F₃OP₂Pt
• 分子量: 679.518
• InChiKey: XCJIIVSKPLVJDC-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  5.75
• 重原子数：
  34.0
• 可旋转键数：
  4.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  [(1,1',2,2'-bisdiphenylphosphinoethane)Pt(CF3)(OH)] 在 苯酚 作用下， 以 四氢呋喃 为溶剂， 以90%的产率得到(1,2-bis(diphenylphosphino)ethane)Pt(CF3)(OPh)
  参考文献：
  名称：

  铂（II）阳离子络合物催化过氧化氢芳烃的羟化反应。铂芳基分子间氧化的证据

  摘要：

  The catalytic hydroxylation of a variety of aromatic substrates is reported using 70% hydrogen peroxide as primary oxidant and a series of (P-P)Pt(CF3)X complexes (P-P = different tetraaryldiphosphines; X = CH2Cl2, -OH, -OPh) as catalysts. The reactivity observed increases with the presence of electron-releasing substituents at the aromatic ring, selectively producing ortho and para products. Good amounts of products are obtained with the most activated substrates phenol, anisole, m-cresol, and 1,3-dimethoxybenzene, and in all cam an interesting ortho selectivity (up to 95%) is observed. A mechanistic study carried out on the last substrate suggests the involvement of an electrophilic metalation of the aromatic ring to produce platinum-aryl intermediates followed by oxygen transfer from a platinum-hydroperoxy species. This seems to represent a rare example in which a soluble transition-metal complex catalyzes the direct hydroxylation of an aromatic ring via electrophilic metalation under mild conditions.

  DOI：

  10.1021/om00059a022
• 作为产物：
  描述：

  [(1,1',2,2'-bisdiphenylphosphinoethane)Pt(CF3)(OOH)] 在 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 生成 [(1,1',2,2'-bisdiphenylphosphinoethane)Pt(CF3)(OH)]
  参考文献：
  名称：

  Synthesis and reactivity of hydroperoxo complexes of platinum(II)

  摘要：

  DOI：

  10.1016/s0020-1693(00)95482-3
• 作为试剂：
  描述：

  苯乙烯 在 [(1,1',2,2'-bisdiphenylphosphinoethane)Pt(CF3)(OH)] 、 双氧水 作用下， 以 四氢呋喃 为溶剂， 生成 氧化苯乙烯
  参考文献：
  名称：

  Pt–Oh物种催化的稀释稀的过氧化氢对末端烯烃的选择性环氧化

  摘要：

  公认在质子介质中起碱的作用的羟基铂（II）配合物，用稀释的H 2 O 2催化末端烯烃的选择性环氧化。

  DOI：

  10.1039/c39840001538

文献信息

• Synthesis of platinum(II)/hydroxycarbonyl complexes and related species and their reactions with hydrogen peroxide: existence of organometallic peroxy acids
  作者：Ivana. Torresan、Rino A. Michelin、Andrea. Marsella、Andrea. Zanardo、Francesco. Pinna、Giorgio. Strukul

  DOI：10.1021/om00049a021

  日期：1991.3.27

  The synthesis and characterization of a class of complexes of the type P2Pt(Rx)(COOH) (P2 = (PPh3)2, (PPh2Me)2, dppe, diphoe, dppp; Rx = CF3, Me, Ph) obtained by insertion of CO into the Pt-OH bond of the corresponding hydroxo complexes is reported, together with their reactivity toward MeOH, P2Pt-(CF3)(OH), and P2Pt(CF3)(OOH) species (P2 = diphosphine). The reaction between PtCOOH and PtOH complexes leads to the formation of CO2-bridged dinuclear species. The reactions of all the carboxy compounds with hydrogen peroxide were studied with the aim of finding a synthetic route to organometallic peroxy acids. Spectroscopic studies suggest the existence of transient hydroperoxy species of the type PtCOO2H; however, attempts to exploit their oxidizing properties in the oxidation of olefins resulted only in the catalytic oxidation of carbon monoxide.
• Preparation and oxygen-transfer properties of novel palladium(II) and platinum(II) hydroperoxo and alkylperoxo complexes
  作者：Giorgio Strukul、Renzo Ros、Rino A. Michelin

  DOI：10.1021/ic00132a006

  日期：1982.2
• A possible molecular pathway for the catalytic oxidation of secondary alcohols to ketones with hydrogen peroxide using platinum(II) complexes as catalysts
  作者：Roberto Zennaro、Francesco Pinna、Giorgio Strukul、Henri Arzoumanian

  DOI：10.1016/0304-5102(91)80126-n

  日期：1991.12

  Attempts to accomplish the oxidation of secondary alcohols to ketones using hydrogen peroxide as oxidants and [(dppe)Pt(CF3)(CH2Cl2)] ClO4 as catalyst are reported. The beta-hydride elimination from an alkoxy complex was shown to produce the corresponding ketone and (dppe)Pt(CF3)H. Oxidation of the Pt-H bond in this complex with H2O2 or (dppe)Pt(CF3)(OOH) yielded (dppe)Pt(CF3)(OH), thereby revealing the possibility of a heterolytic catalytic pathway. Attempts to carry out the catalytic oxidation of a variety of alcohols produced appreciable amounts of ketones, but the reaction was recognized, with one significant exception, to be essentially homolytic in nature.
• Baeyer-Villiger oxidation of cyclic ketones with hydrogen peroxide catalyzed by cationic complexes of platinum(II): selectivity properties and mechanistic studies
  作者：Marino Del Todesco Frisone、Francesco Pinna、Giorgio Strukul

  DOI：10.1021/om00025a027

  日期：1993.1