bis(dimethylphenylphosphine)(diphenylacetylene)platinum | 211870-85-8

• 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: bis(dimethylphenylphosphine)(diphenylacetylene)platinum
• 英文别名: Dimethyl(phenyl)phosphane;2-phenylethynylbenzene;platinum
• CAS: 211870-85-8
• 化学式: C₃₀H₃₂P₂Pt
• 分子量: 649.612
• InChiKey: SCXIKZZZUNWDKJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.19
• 重原子数：
  33
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  cis-[bis(dimethylphenylphosphane)dichlroplatinum(II)] 以 四氢呋喃 、 氘代苯 、 苯 为溶剂， 生成 bis(dimethylphenylphosphine)(diphenylacetylene)platinum
  参考文献：
  名称：

  铂催化炔烃与有机二锗烷和环状寡锗烷的双锗化

  摘要：

  六甲基二锗烷，Me3GeGeMe3，在铂配合物的存在下，在 120°C 下与各种炔烃反应，以中等至良好的产率得到 Z-1,2-双（锗基）乙烯。末端炔烃比内部炔烃表现出更高的反应性。[Pt(acac)2] 和 [Pt(dba)2] 作为有效的催化剂，而 [Pt(PPh3)4]、[PtCl2(PPh3)2] 和 [Pt(dba)2]-亚磷酸酯被发现不活跃。四元和六元环状低锗烷，例如十二甲基环六锗烷 (Me2Ge)6，在铂催化剂存在下与炔烃反应，生成约 1,4-二元环六-2,5-二烯。30% 的收率。苯乙炔与 1,2-digermacyclohexa-3,5-diene 的反应以 93% 的产率得到相应的 1,4-digermacycloocta-2,5,7-trienes。已经制备了具有各种叔膦配体的双（锗基）铂配合物作为上述炔烃催化双锗化的关键中间体模型，并通过光谱方法和 X 射线晶体学确定了它们的结构。双

  DOI：

  10.1246/bcsj.74.123

文献信息

• Kinetic Studies on the Reductive Elimination of <i>cis</i>-PtMe(SiPh₃)(PMe₂Ph)₂ and <i>cis</i>-PtMe(GePh₃)(PMe₂Ph)₂. The First Comparison between C−Si and C−Ge Reductive Elimination
  作者：Fumiyuki Ozawa、Toshihiko Hikida、Koh Hasebe、Takuya Mori

  DOI：10.1021/om970841n

  日期：1998.3.1

  of the SiPh3 ligand and only slightly higher than that of the Me ligand, the GePh3 ligand was found to possess a much higher trans effect than the methyl ligand, comparable to the SiPh3 ligand. Thermolysis of 1b and 2b in toluene-d8 in the presence of an excess amount of diphenylacetylene provided quantitative yields of reductive-elimination products MeSiPh3 and MeGePh3, respectively. Kinetic studies

  新型复合物顺式-PtMe（GePh 3）（PMe 2 Ph）2（2b）的制备方法是：先用2当量的MeLi在THF中处理反式-PtCl（GePh 3）（PMe 2 Ph）2（3），然后反应体系的甲醇分解。2b的X射线和NMR数据，以及相关的cis -PtMe（SiPh 3）（PMe 2 Ph）2（1b）和cis -PtMe 2（PMe 2 Ph）2（4）的NMR数据），表示的反式影响顺序如下：SIPH 3 »GePh 3 >我。虽然GePh的反影响3配体多比SIPH的降低3配体和仅比我配体，所述GePh稍高3配体被发现具有比甲基配体高得多的反式作用，可比SiPh 3配体。热解的图1b和2b中在甲苯d 8中的二苯基乙炔过量的存在提供的还原消除产品定量的产率MeSiPh 3和MeGePh 3， 分别。动力学研究表明，甲基-锗烷基复合物2b比甲基-甲硅烷基复合物1b稳定得多。两种络合物的还原消除是
• Thermolysis Reactions of <i>cis</i>-PtR(SiPh₃)(PMe₂Ph)₂ in Solution
  作者：Koh Hasebe、Jun Kamite、Takuya Mori、Hiroyuki Katayama、Fumiyuki Ozawa

  DOI：10.1021/om000012t

  日期：2000.5.1

  A series of trans- and cis-PtR(SiPh3)(PMe2Ph)(2) complexes have been prepared and their thermolysis reactions in solution examined. The trans isomers (R = Me, Et) are robust, and only the methyl complex affords MeSiPh3 as the reductive elimination product in 72-82% yields. In contrast, the cis isomers (R = Me, Et, Pr, Bu) form the corresponding alkylsilanes in almost quantitative yields (>97%). Despite the selective formation of the reductive elimination products, the cis-alkyl-silyl complexes bearing beta-hydrogens undergo a rapid repetition of the beta-hydrogen elimination and insertion processes, as confirmed by a deuterium-labeling experiment using cis-Pt(CH2CD3)(SiPh3)(PMe2Ph)(2). The alkylsilane formation from the cis isomers proceeds via two reaction paths. One is the direct C-Si reductive elimination. On the other path, the cis-PtR(SiPh3)(PMe2Ph)(2) complexes are initially isomerized to the corresponding cis-PtPh(SiRPh2)(PMe2Ph)(2) complexes by the exchange of the Pt-R group with the Si-Ph group, and the resulting phenyl-silyl complexes reductively eliminate alkylsilanes. The methyl-silyl complex decomposes exclusively by the former path, while the other alkyl-silyl complexes (R = Et, Pr, Bu) follow mainly the latter path. Preparation and thermolysis reaction of the related cis-PtEt(GePh3)(PMe2Ph)(2) are also reported.