trans-[Pt(H)(FHF)(PCy3)2] | 144717-67-9

• 英文名称: trans-[Pt(H)(FHF)(PCy3)2]
• CAS: 144717-67-9
• 化学式: C₃₆H₆₈F₂P₂Pt
• 分子量: 795.96
• InChiKey: YEKINJVUKRVHBQ-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：
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• 环数：
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• 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：

  trans-[Pt(H)(FHF)(PCy3)2] 、 三氟甲磺酸三甲基硅酯 以 四氢呋喃 为溶剂， 以80%的产率得到trans-[Pt(PCy3)2H(OTf)]
  参考文献：
  名称：

  Hydrogen Bonding in Transition Metal Complexes:  Synthesis, Dynamics, and Reactivity of Platinum Hydride Bifluoride Complexes

  摘要：

  Platinum hydride bifluoride (FHF) complexes trans-[Pt(PR3)(2)H(FHF)] (R = CY, Pr-i) were prepared from the reaction of the corresponding trans-dihydride complexes with NEt3. 3(HF) in THF. They were also formed in C-F activation reactions of the same precursors with C6F6 in the presence of [Me4N]F. The low-temperature NMR spectra exhibit a complete network of coupling between the spin 1/2 nuclei, H-1, P-31, F-19, and Pt-195. At higher temperatures, fluxional behavior is observed which is principally associated with intermolecular exchange of HF between platinum centers. However, satisfactory simulation of the spectra also requires inclusion of intermolecular exchange of the distal fluoride. Addition of [Bu4N]FHF results in coalescence of the bifluoride proton resonance of the complex and the added bifluoride, demonstrating that the bifluoride ligand can exchange with free bifluoride, FHF-. The IR spectrum of trans-[Pt(PCy3)(2)H(FHF)] shows two broad bands at 2604 and 1832 cm(-1) assigned to the H-F stretching modes and a sharp band at 2272 cm(-1) for the Pt-H stretching mode. Bifluoride is a weakly coordinated ligand which can be replaced to give trans[Pt(PCy3)(2)(H)X] complexes where X = N-3,OTf. Hydrogen fluoride may be removed from trans-[Pt(PCy3)(2)H(FHF)] by treatment with CsOH in the presence of [NMe4]F, yielding trans-[Pt(PCy3)(2)(H)F]. In addition, these bifluoride complexes fluorinate organic compounds, such as CH3I, CH3COCl, and C6H5COCl, to give CH3F, CH3COF, and C6H5COF together with trans-[Pt(PCy3)(2)(H)X] (X = Cl, I). Reactions with PPh3 and pyridine yield trans-[Pt(PCy3)(2)(PPh3)H]FHF and trans- [Pt(PCy3)(2)(C5H5N)H]FHF.

  DOI：

  10.1021/ja0010913
• 作为产物：
  描述：

  trans-dihydridobis(tricyclohexylphosphine)platinum 、 triethylamine tris(hydrogen fluoride) 以 四氢呋喃 为溶剂， 以76%的产率得到trans-[Pt(H)(FHF)(PCy3)2]
  参考文献：
  名称：

  Hydrogen Bonding in Transition Metal Complexes:  Synthesis, Dynamics, and Reactivity of Platinum Hydride Bifluoride Complexes

  摘要：

  Platinum hydride bifluoride (FHF) complexes trans-[Pt(PR3)(2)H(FHF)] (R = CY, Pr-i) were prepared from the reaction of the corresponding trans-dihydride complexes with NEt3. 3(HF) in THF. They were also formed in C-F activation reactions of the same precursors with C6F6 in the presence of [Me4N]F. The low-temperature NMR spectra exhibit a complete network of coupling between the spin 1/2 nuclei, H-1, P-31, F-19, and Pt-195. At higher temperatures, fluxional behavior is observed which is principally associated with intermolecular exchange of HF between platinum centers. However, satisfactory simulation of the spectra also requires inclusion of intermolecular exchange of the distal fluoride. Addition of [Bu4N]FHF results in coalescence of the bifluoride proton resonance of the complex and the added bifluoride, demonstrating that the bifluoride ligand can exchange with free bifluoride, FHF-. The IR spectrum of trans-[Pt(PCy3)(2)H(FHF)] shows two broad bands at 2604 and 1832 cm(-1) assigned to the H-F stretching modes and a sharp band at 2272 cm(-1) for the Pt-H stretching mode. Bifluoride is a weakly coordinated ligand which can be replaced to give trans[Pt(PCy3)(2)(H)X] complexes where X = N-3,OTf. Hydrogen fluoride may be removed from trans-[Pt(PCy3)(2)H(FHF)] by treatment with CsOH in the presence of [NMe4]F, yielding trans-[Pt(PCy3)(2)(H)F]. In addition, these bifluoride complexes fluorinate organic compounds, such as CH3I, CH3COCl, and C6H5COCl, to give CH3F, CH3COF, and C6H5COF together with trans-[Pt(PCy3)(2)(H)X] (X = Cl, I). Reactions with PPh3 and pyridine yield trans-[Pt(PCy3)(2)(PPh3)H]FHF and trans- [Pt(PCy3)(2)(C5H5N)H]FHF.

  DOI：

  10.1021/ja0010913

文献信息

• Electron transfer reactions involving trans-[PtH2(PCy3)2] and fluorinated benzonitriles
  作者：Samuel Hintermann、Paul S. Pregosin、Heinz Rüegger、Howard C. Clark

  DOI：10.1016/0022-328x(92)83474-v

  日期：1992.2

  trans-[PtH2(PCy3)2] reacts with activated benzonitriles such as 4-R-C6F4CN (R = F, H, CN, OCH3) bearing electron-withdrawing substituents to give the new platinum(II) aryl complexes trans-[PtHRC6F3CN(PCy3)2], which have been isolated and fully characterized, and a hydridofluoride trans-[PtH(“F”)(PCy3)2], where “F” is either F or HF2, which has been detected in solution. These complexes and related by-products

  复杂的反式-[PtH 2（PCy 3）2 ]与带有吸电子取代基的活化苄腈如4-RC 6 F 4 CN（R = F，H，CN，OCH 3）反应生成新的铂（II） ）芳基配合物反式-[PtHRC 6 F 3 CN（PCy 3）2 ]，已被分离并充分表征，氟化氢反式-[PtH（“ F”）（PCy 3）2 ]，其中“ F”为F或HF 2，已在解决方案中检测到。通过一维和二维多核NMR光谱对反应中的这些络合物和相关副产物进行了表征。基于以下条件，提出了一种反应机理，该反应机理涉及速率确定电子从二酐络合物到有机底物的转移：（i）腈的相对反应速率（p -C 6 F 4（CN）2 > C 6 F 5 CN > p -C 6 HF 4 CN> p -C 6 F 4（OCH 3）CN> o，o -C 6 H 3F 2 CN），其平行于它们的电子亲和力；（ii）用PBN“自旋捕获”后，通过ESR光谱观察自由基。
• Contrasting Reactivity of Fluoropyridines at Palladium and Platinum:  C−F Oxidative Addition at Palladium, P−C and C−F Activation at Platinum
  作者：Naseralla A. Jasim、Robin N. Perutz、Adrian C. Whitwood、Thomas Braun、Joseph Izundu、Beate Neumann、Sascha Rothfeld、Hans-Georg Stammler

  DOI：10.1021/om049448p

  日期：2004.12.1

  behavior of palladium(0) and platinum(0) is revealed in the reactivity of [M(PR3)2] (M = Pd or Pt; R = Cy or iPr) toward pentafluoropyridine and 2,3,5,6-tetrafluoropyridine. The palladium complexes react with pentafluoropyridine at 100 °C to yield the fluoride complexes trans-[Pd(F)(4-C5NF4)(PR3)2]. They do not react with 2,3,5,6-tetrafluoropyridine. The reaction of platinum(0) complexes [Pt(PR3)2] with

  钯（0）和铂（0）的发散行为在[M（PR 3）2 ]（M = Pd或PT; R = Cy或iPr）朝向五氟吡啶和2,3,5,6-四氟吡啶。钯配合物与五氟吡啶在100°C下反应，生成反式-[Pd（F）（4-C 5 NF 4）（PR 3）2 ]的氟化物配合物。它们不与2,3,5,6-四氟吡啶反应。在室温下，铂（0）配合物[PT（PR 3）2 ]与五氟吡啶在THF中的反应生成反式[[PT（R）（4-C 5 NF 4）（PR 3）（PFR 2）]配合物，而[PT（PCy 3）2]与2,3,5,6-四氟吡啶一起导致CH活化，形成顺式-[PT（H）（4-C 5 NF 4）（PCy 3）2 ]；该配合物可通过光解转化为反式异构体。与c是-hydride也[PT（PCY的反应过程中形成3）2 ]使用C 5 NF 5于己烷中。这些反应也与先前对相同底物对Ni（PEt 3）2 }的反应性的研究形成对比，后者产生了[Ni（F）（2-C