(((C2F5)2PCH2)2)Pt(Me)(trifluoroacetate) | 163859-33-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (((C2F5)2PCH2)2)Pt(Me)(trifluoroacetate)
• 英文别名: (dfepe)Pt(Me)(O2CCF3)；[PtMe(trifluoroacetato)(bis(di(perfluoroethyl)phosphino)ethane)]；2-[bis(1,1,2,2,2-pentafluoroethyl)phosphanyl]ethyl-bis(1,1,2,2,2-pentafluoroethyl)phosphane;carbanide;platinum(2+);2,2,2-trifluoroacetate
• CAS: 163859-33-4
• 化学式: C₁₃H₇F₂₃O₂P₂Pt
• 分子量: 889.188
• InChiKey: OGKXOCWVSNPCQB-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  (((C2F5)2PCH2)2)Pt(Me)(trifluoroacetate) 、 三氟化硼 以 二氯甲烷-D2 为溶剂， 生成 [PtMe(trifluoroacetato)(BF3)(bis(di(perfluoroethyl)phosphino)ethane)]
  参考文献：
  名称：

  Synthesis of [(dfepe)Pt(Me)(NC₅F₅)]⁺B(C₆F₅)₄⁻, a Highly Active Ethylene Dimerization Catalyst

  摘要：

  The synthesis of cationic adducts (dfepe)Pt(Me)(L)(+) (dfepe = (C2F5)(2)PCH2CH2P(C2F5)(2); L = MeCN, CO, C2H4, C5F5N, mu-Cl) are reported. Treatment of (cod)Pt(Me)Cl with AgSbF6 in acetonitrile followed by the addition of dfepe afforded (dfepe)Pt(Me)(CH3CN)+SbF6-. Addition of B(C-6F5)(3) to (dfepe)Pt(Me)(O2CCF3) in methylene chloride afforded the structurally characterized borane association product (dfepe)Pt(Me)[(O2CCF3)B(C6F5)(3)] in high yield. Attempts to displace the [(O2CCF3)B(C6F5)(3)](-) anion with donor ligands resulted in loss of borane and regeneration of (dfepe)Pt(Me)(O2CCF3). Addition of the mesitylenium acid (1,3,5-C6H4Me3)B+(C6F5)(4)(-) to (dfepe)PtMe2 in methylene chloride at ambient temperatures resulted in chloride abstraction and the precipitation of the chloride-bridged dimeric complex [{(dfepe)Pt(Me)}(2)(mu-Cl)]B+(C6F5)(4)(-), which has been structurally characterized. In contrast, treatment of (dfepe)PtMe2 with (1,3,5-C6H4Me3)B+(C6F5)(4)(-) in pentafluoropyridine at ambient temperature resulted in the precipitation of the structurally characterized pentafluoropyridine adduct [(dfepe)Pt(Me)(NC5F5)]B+(C6F5)(4)(-) in good yield. Exposure of [(dfepe)Pt(Me)(NC5F5)]B+(C6F5)(4)(-) to 1 atm of CO in o-difluorobenzene gave the carbonyl complex [(dfepe)Pt(Me)(CO)]B+(C6F5)(4)(-). In marked contrast to previously reported platinum systems, [(dfepe)Pt(Me)(NC5F5)]+B(C6F5)(4)(-) is a very active ethylene dimerization catalyst at ambient temperature (600 psi ethylene, 22 degrees C in ortho-difluorobenzene, 150 turnovers h(-1)). The ethylene adduct [(dfepe)Pt(Me)(eta(2) -C2H4)]B+(C6F5)(4)(-) has been spectroscopically characterized at -20 degrees C.

  DOI：

  10.1021/om8003509
• 作为产物：
  描述：

  [PtMe(trifluoroacetato)(B(C₆F₅)3)(bis(di(perfluoroethyl)phosphino)ethane)] 在 CO 作用下， 以 not given 为溶剂， 生成 (((C2F5)2PCH2)2)Pt(Me)(trifluoroacetate)
  参考文献：
  名称：

  Synthesis of [(dfepe)Pt(Me)(NC₅F₅)]⁺B(C₆F₅)₄⁻, a Highly Active Ethylene Dimerization Catalyst

  摘要：

  The synthesis of cationic adducts (dfepe)Pt(Me)(L)(+) (dfepe = (C2F5)(2)PCH2CH2P(C2F5)(2); L = MeCN, CO, C2H4, C5F5N, mu-Cl) are reported. Treatment of (cod)Pt(Me)Cl with AgSbF6 in acetonitrile followed by the addition of dfepe afforded (dfepe)Pt(Me)(CH3CN)+SbF6-. Addition of B(C-6F5)(3) to (dfepe)Pt(Me)(O2CCF3) in methylene chloride afforded the structurally characterized borane association product (dfepe)Pt(Me)[(O2CCF3)B(C6F5)(3)] in high yield. Attempts to displace the [(O2CCF3)B(C6F5)(3)](-) anion with donor ligands resulted in loss of borane and regeneration of (dfepe)Pt(Me)(O2CCF3). Addition of the mesitylenium acid (1,3,5-C6H4Me3)B+(C6F5)(4)(-) to (dfepe)PtMe2 in methylene chloride at ambient temperatures resulted in chloride abstraction and the precipitation of the chloride-bridged dimeric complex [{(dfepe)Pt(Me)}(2)(mu-Cl)]B+(C6F5)(4)(-), which has been structurally characterized. In contrast, treatment of (dfepe)PtMe2 with (1,3,5-C6H4Me3)B+(C6F5)(4)(-) in pentafluoropyridine at ambient temperature resulted in the precipitation of the structurally characterized pentafluoropyridine adduct [(dfepe)Pt(Me)(NC5F5)]B+(C6F5)(4)(-) in good yield. Exposure of [(dfepe)Pt(Me)(NC5F5)]B+(C6F5)(4)(-) to 1 atm of CO in o-difluorobenzene gave the carbonyl complex [(dfepe)Pt(Me)(CO)]B+(C6F5)(4)(-). In marked contrast to previously reported platinum systems, [(dfepe)Pt(Me)(NC5F5)]+B(C6F5)(4)(-) is a very active ethylene dimerization catalyst at ambient temperature (600 psi ethylene, 22 degrees C in ortho-difluorobenzene, 150 turnovers h(-1)). The ethylene adduct [(dfepe)Pt(Me)(eta(2) -C2H4)]B+(C6F5)(4)(-) has been spectroscopically characterized at -20 degrees C.

  DOI：

  10.1021/om8003509

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.
• Bennett, Byron L.; Roddick, Dean M., Inorganic Chemistry, 1996, vol. 35, # 16, p. 4703 - 4707
  作者：Bennett, Byron L.、Roddick, Dean M.

  DOI：——

  日期：——
• Protonation studies of electrophilic platinum(II) alkyl complexes: synthesis and characterization of (dfepe)Pt(Me)X (X = O2CCF3, OSO2CF3, OSO3H)
  作者：Byron L. Bennett、Jerry Birnbaum、Dean M. Roddick

  DOI：10.1016/0277-5387(94)00366-m

  日期：1995.1

  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).
• Thermal elimination reactions of (dfepe)Pt(CF3)X (fluoroalkyl)phosphine complexes (X = Cl, O2CCF3): synthesis and structural characterization of an unusual chelate-bridged platinum(0) complex, [(dfepe)Pt(CO)]2(μ-dfepe)
  作者：R.Gregory Peters、Byron L. Bennett、Dean M. Roddick

  DOI：10.1016/s0020-1693(97)05692-2

  日期：1997.11

  Platinum trifluoromethyl-substituted (fluoroalkyl) phosphine complexes (dfepe)Pt(CF3) (X) (dfepe = (C2F5)(2)PCH2CH2P(C2F5)(2), X = Cl, O2CCF3) have been prepared from the corresponding cyclooctadiene precursors, (cod)Pt(CF3) (X), and have been fully characterized by F-19 and P-31 NMR spectroscopy. Thermolyses of (dfepe)Pt(CF3) X complexes in acetone at 100 degrees lead to elimination and disproportionation to give (dfepe)(2)Pt and unidentified Pt(O) products. In the presence of carbon monoxide, an initial dfepe loss prior to Pt-CF3 elimination is observed and subsequent trapping by dfepe and CO produces (dfepe)Pt(CO)(2). In the presence of additional dfepe, (dfepe)Pt(CO)(2) reacts further after cooling to ultimately afford a new platinum(O) carbonyl dfepe-bridged dimer, [(dfepe)Pt(CO)](2)(mu-dfepe). Crystallographic data for this molecule reveals an unusual distorted-tetrahedral platinum coordination environment and a dfepe-bridged geometry. Crystal data for [(dfepe)Pt(CO)](2)(mu-dfepe): triclinic, P (1) over bar (No. 2), a = 8.802(2), b = 10.581(2), c = 16.506(3) Angstrom, alpha = 74.75(3), beta = 78.03(3),gamma = 78.30(3)degrees, V = 1432.9(5) Angstrom(3), Z = 1, R = 0.0337, wR(2) = 0.0858. (C) 1997 Elsevier Science S.A.