[(triphos)PtMe][BF₄] | 900523-16-2

• 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: [(triphos)PtMe][BF₄]
• 英文别名: [PtMe(bis(2-diphenylphosphinoethyl)phenylphosphine)](tetrafluoroborate)；bis(2-diphenylphosphanylethyl)-phenylphosphane;carbanide;platinum(2+);tetrafluoroborate
• CAS: 900523-16-2
• 化学式: BF₄*C₃₅H₃₆P₃Pt
• 分子量: 831.477
• InChiKey: WETYVXNOAHKTSV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.81
• 重原子数：
  44
• 可旋转键数：
  11
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  [(triphos)PtMe][BF₄] 在 diphenylammonium tetrafluoroborate 、 cesium fluoride 作用下， 以 乙腈 为溶剂， 反应 26.0h， 生成
  参考文献：
  名称：

  Promoting C–C Bond Coupling of Benzyne and Methyl Ligands in Electron-Deficient (triphos)Pt–CH₃⁺ Complexes

  摘要：

  In situ generated benzyne reacts at room temperature with (triphos)Pt-CH3+ to form a five-coordinate p-complex (2) that is isolable and stable in solution. Thermolysis of 2 at 60 degrees C generates (triphos)Pt(o-tolyl)(+) (3), which is the product of formal migratory insertion of CH3 onto the coordinated benzyne. The reaction of 2 with the acid Ph2NH2+ yields toluene at room temperature over the course of 8 h, while the same reaction with 3 only proceeds to 40% conversion over 2 days. These data indicate that the protonolysis of 2 does not proceed by CH3 migration onto benzyne to form 3 followed by protodemetalation. Instead, the data suggest either that protonation of 2 is first and is followed by H migration to yield a (PtPh)-Ph-IV(Me) dication or that this latter species is generated by direct protonolysis of coordinated benzyne prior to reductive elimination of toluene.

  DOI：

  10.1021/acs.organomet.5b00121
• 作为产物：
  描述：

  [(triphos)PtMe(C₆H₄)][BF₄] 反应 72.0h， 生成 [(triphos)PtMe][BF₄] 、 [(triphos)Pt(2-Me)Ph][BF₄]
  参考文献：
  名称：

  Promoting C–C Bond Coupling of Benzyne and Methyl Ligands in Electron-Deficient (triphos)Pt–CH₃⁺ Complexes

  摘要：

  In situ generated benzyne reacts at room temperature with (triphos)Pt-CH3+ to form a five-coordinate p-complex (2) that is isolable and stable in solution. Thermolysis of 2 at 60 degrees C generates (triphos)Pt(o-tolyl)(+) (3), which is the product of formal migratory insertion of CH3 onto the coordinated benzyne. The reaction of 2 with the acid Ph2NH2+ yields toluene at room temperature over the course of 8 h, while the same reaction with 3 only proceeds to 40% conversion over 2 days. These data indicate that the protonolysis of 2 does not proceed by CH3 migration onto benzyne to form 3 followed by protodemetalation. Instead, the data suggest either that protonation of 2 is first and is followed by H migration to yield a (PtPh)-Ph-IV(Me) dication or that this latter species is generated by direct protonolysis of coordinated benzyne prior to reductive elimination of toluene.

  DOI：

  10.1021/acs.organomet.5b00121

文献信息

• Steric Crowding Makes Challenging C_sp3–F Reductive Eliminations Feasible
  作者：Shu-Bin Zhao、Jennifer J. Becker、Michel R. Gagné

  DOI：10.1021/om200515f

  日期：2011.8.8

  A high-yielding fluorination of (triphos)Pt-R+ has been achieved using an array of F+ sources, with XeF2 yielding R-F in minutes. The C-F coupling proved to be a stereoretentive process that proceeds via a concerted reductive elimination from a putative dicationic Pt(IV) center. The larger the steric congestion of the (triphos)Pt-C-sp3(+) complexes, the more efficient the fluorination, seemingly a result of sterically accelerated C-F reductive elimination along with simultaneous deceleration of its competing processes (beta-H elimination).
• Protonolysis of Cationic Pt−C Bonds with Mild Acids:  Can Ligand Torsional Effects Speed Associative Processes?
  作者：Jeremy A. Feducia、Alison N. Campbell、Jeffrey W. Anthis、Michel R. Gagné

  DOI：10.1021/om051066b

  日期：2006.6.1

  Tridentate phosphine pincer ligands facilitate the protonolysis of cationic Pt-CH3 compounds ( to Pt dications and CH4) with the ammonium acid Ph2NH2 center dot BF4. Large rate enhancements over nonpincer analogues (> 50 000) are observed. A mechanism is proposed wherein ring strain present in the planar ground-state arrangement of three phosphine ligands is released in putative five-coordinate intermediates and transition states.