(dfepe)Pt(Me)(OSO2CF3) | 163859-34-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: (dfepe)Pt(Me)(OSO2CF3)
• 英文别名: (((C2F5)2PCH2)2)Pt(Me)(OTf)；2-[bis(1,1,2,2,2-pentafluoroethyl)phosphanyl]ethyl-bis(1,1,2,2,2-pentafluoroethyl)phosphane;carbanide;platinum(2+);trifluoromethanesulfonate
• CAS: 163859-34-5
• 化学式: C₁₂H₇F₂₃O₃P₂PtS
• 分子量: 925.243
• InChiKey: QJEHCTFVROWWJQ-UHFFFAOYSA-M

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：

  (dfepe)Pt(Me)(OSO2CF3) 、 三氟甲磺酸 以 二氯甲烷-D2 为溶剂， 生成
  参考文献：
  名称：

  Protonation studies of electrophilic platinum(II) alkyl complexes: synthesis and characterization of (dfepe)Pt(Me)X (X = O2CCF3, OSO2CF3, OSO3H)

  摘要：

  The platinum methyl complexes (dfepe)Pt(Me)X (dfepe = (C2F5)(2)PCH2 CH2P(C2F5)2(,) X = O2CCF3, OSO2CF3, OSO3H) have been prepared by the reaction of (dfepe)Pt(Me), with an excess of the corresponding acid, HX. These compounds have been characterized by H-1, F-19 and P-31 NMR data. (dfepe)Pt(Me)(2) and (dfepe)Pt(Me) (OSO2CF3) have also been characterized in the solid state by X-ray diffraction. Both of these compounds exhibit short Pt-Me bonds, consistent with the highly electrophilic nature of the (dfepe)Pt moiety. In contrast to analogous donor phosphine systems (R(3)P)(2)Pt(Me)(2), which undergo complete protonolysis and methane loss by HX at -78 degrees C to give (R(3)P)(2)Pt(X)(2), (dfepe)Pt(Me)X complexes are remarkably stable to further protonolysis even in neat strong acid media. In dichloromethane, treatment of (dfepe)Pt(Me)(OSO2CF3) with excess CF3SO3H results in the association of one equivalent of acid with the bound triflate ligand to form (dfepe)Pt(Me)((OTf)(2)H).

  DOI：

  10.1016/0277-5387(94)00366-m
• 作为产物：
  描述：

  [PtMe2(bis(di(perfluoroethyl)phosphino)ethane)] 、 三氟甲磺酸 以 二氯甲烷 为溶剂， 以87%的产率得到(dfepe)Pt(Me)(OSO2CF3)
  参考文献：
  名称：

  Protonation studies of electrophilic platinum(II) alkyl complexes: synthesis and characterization of (dfepe)Pt(Me)X (X = O2CCF3, OSO2CF3, OSO3H)

  摘要：

  The platinum methyl complexes (dfepe)Pt(Me)X (dfepe = (C2F5)(2)PCH2 CH2P(C2F5)2(,) X = O2CCF3, OSO2CF3, OSO3H) have been prepared by the reaction of (dfepe)Pt(Me), with an excess of the corresponding acid, HX. These compounds have been characterized by H-1, F-19 and P-31 NMR data. (dfepe)Pt(Me)(2) and (dfepe)Pt(Me) (OSO2CF3) have also been characterized in the solid state by X-ray diffraction. Both of these compounds exhibit short Pt-Me bonds, consistent with the highly electrophilic nature of the (dfepe)Pt moiety. In contrast to analogous donor phosphine systems (R(3)P)(2)Pt(Me)(2), which undergo complete protonolysis and methane loss by HX at -78 degrees C to give (R(3)P)(2)Pt(X)(2), (dfepe)Pt(Me)X complexes are remarkably stable to further protonolysis even in neat strong acid media. In dichloromethane, treatment of (dfepe)Pt(Me)(OSO2CF3) with excess CF3SO3H results in the association of one equivalent of acid with the bound triflate ligand to form (dfepe)Pt(Me)((OTf)(2)H).

  DOI：

  10.1016/0277-5387(94)00366-m

文献信息

• Organometallics in Acidic Media:  Catalytic Dimerization of Ethylene by (Perfluoroalkyl)phosphine Complexes of Platinum and Palladium in Trifluoroacetic Acid
  作者：Shannon White、Byron L. Bennett、Dean M. Roddick

  DOI：10.1021/om990179q

  日期：1999.6.1

  and ethylene ligand exchange results in catalytic vinylic H+/D+ exchange with CF3CO2D (t1/2 ≈ 40 min). Analogous palladium systems exhibit enhanced dimerization activity at 25 °C (340 turnovers/h, 100 psi C2H4) and form (dfepe)2Pd as a catalyst resting state. Inhibition of catalytic activity in the presence of added dfepe was noted. Comparisons between catalytic runs in CF3CO2H and CF3CO2D gave an apparent

  描述了通过（dfepe）Pt（Me）X络合物在质子惰性和三氟乙酸溶剂中的催化乙烯二聚作用。在CH 2氯2，催化剂失活是由于酸损失和代（dfepe）的Pt（η 2 -C 2 H ^ 4）中观察到。相反，长期的乙烯二聚活性发生在80°C的三氟乙酸中，并产生2-（三氟乙酰基）丁烷作为唯一的有机产物。在这些反应条件下，催化剂的静止状态为（dfepe）Pt（Et）（O 2 CCF 3）。在20°C下，从（dfepe）Pt（Et）（O 2 CCF 3）和乙烯配体交换中可逆的酸消除导致催化乙烯基H +/ D +与CF 3 CO 2 D交换（t 1/ 2≈40分钟）。相似的钯体系在25°C（340次循环/小时，100 psi C 2 H 4）下表现出增强的二聚活性，并以（dfepe）2 Pd形式存在于催化剂中。注意到在添加的dfepe存在下催化活性的抑制。在CF 3 CO 2 H和CF 3 CO 2 D中
• Metal−Alkyl Bond Protonolysis Studies of (dfepe)Pt(Me)X Complexes in Acidic Media
  作者：Byron L. Bennett、Justin M. Hoerter、James F. Houlis、Dean M. Roddick

  DOI：10.1021/om990743x

  日期：2000.2.1

  Protonolyses of (dfepe)Pt(Me)X (dfepe = (C2F5)(2)PCH2CH2P(C2F5)(2); X = O2CCF3, OSO2H, OSO2CF3, OSO2F) complexes in their respective neat acid solutions cleanly yield (dfepe)Pt(X)(2) products with rates dependent on relative acid strengths. No (dfepe)Pt(Me)(X)(2)(H)(+) intermediates were observed by variable-temperature. NMR in dichloromethane. The (perfluoroaryl)phosphine analogue (dfppe)Pt(Me)(2) (dfppe = (C6F5)(2)PCH2CH2P(C6F5)(2)) is much less resistant to protonolysis and rapidly converts to (dfppe)Pt(OTf)(2) in HOTf at 20 degrees C. Kinetic studies for protonolysis in CF3CO2H(D) and CF3SO3H(D) solvents were carried out. Examination of ionic strength and chloride anion effects in trifluoroacetic acid indicate that prior association of anion to (dfepe)Pt(Me)X systems is not kinetically important. k(H)/k(D) values were obtained from competitive protonolysis studies (CF3CO2H, 9 +/- 2 (20 degrees C); H2SO4, 7 +/- 2 (100 degrees C); CF3SO3H, 2.7 +/- 0.7 (100 degrees C)). In the case of CF3CO2H, separate kinetic runs in protio and deuterio acids gave a lower k(H)/k(D) value of 3.6(4). The data obtained in these studies do not differentiate between limiting S(E)2 and S-E(oxidative) protonolysis mechanisms.