| 105639-79-0

• CAS: 105639-79-0
• 化学式: C₃₆H₃₆NP₃Pt
• 分子量: 770.69
• InChiKey: XKOSFBKUZBCSFL-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：
  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

• 作为产物：
  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

文献信息

• Epoxidation versus Baeyer−Villiger Oxidation: The Possible Role of Lewis Acidity in the Control of Selectivity in Catalysis by Transition Metal Complexes
  作者：Agostino Brunetta、Giorgio Strukul

  DOI：10.1002/ejic.200300584

  日期：2004.3

  as the fourth ligand is reported. The complexes are characterized by IR and 31P1H} NMR spectroscopy and by molar conductivity data, and their Lewis acid characteristics determined by NMR techniques. All complexes are good catalysts for the epoxidation of olefins and the Baeyer−Villiger oxidation of ketones under mild conditions using hydrogen peroxide as oxidant. The latter reaction is more Lewis-acid

  据报道，合成了一系列含有 triphos 或 triphosPO 以及溶剂、羟基或氢过氧作为第四配体的 PtII 阳离子配合物。配合物通过 IR 和 31P1H} NMR 光谱和摩尔电导率数据表征，并通过 NMR 技术确定它们的路易斯酸特性。所有配合物都是在温和条件下使用过氧化氢作为氧化剂进行烯烃环氧化和酮的 Baeyer-Villiger 氧化的良好催化剂。就催化剂的电子特性而言，后一种反应对路易斯酸的要求更高。路易斯酸性金属中心的使用允许不饱和酮选择性氧化为相应的不饱和酯，而不会氧化碳碳双键，表明催化剂的强路易斯酸特性可能是设计能够分离两种过程的催化剂的重要特征。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)