bis(1,2-bis(diphenylphosphinoethynyl)benzene)palladium(0)*CH2Cl2 | 265114-79-2

• 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: bis(1,2-bis(diphenylphosphinoethynyl)benzene)palladium(0)*CH2Cl2
• 英文别名: Pd(dppeb)2*CH2Cl2；Pd(1,2-bis(diphenylphosphinoethynyl)benzene)2*CH2Cl2
• CAS: 265114-79-2
• 化学式: CH₂Cl₂*C₆₈H₄₈P₄Pd
• 分子量: 1180.38
• InChiKey: HKZIJOVHQZWHKF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.56
• 重原子数：
  76.0
• 可旋转键数：
  8.0
• 环数：
  12.0
• sp3杂化的碳原子比例：
  0.01
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  1,2-bis(diphenylphosphinoethynyl)benzene 在 hydrazine 作用下， 以 二氯甲烷 、 苯 为溶剂， 生成 bis(1,2-bis(diphenylphosphinoethynyl)benzene)palladium(0)*CH2Cl2
  参考文献：
  名称：

  Structure and Thermal Reactivity of a Novel Pd(0) Metalloenediyne

  摘要：

  We report the X-ray diffraction structure and thermal reactivity of the metalloenediyne compound bis(1,2-bis(diphenylphosphinoethynyl)benzenepalladium(0) (Pd(dppeb)(2), 1). The structure of 1 features a tetrahedral Pd(0) center with four phosphorus atoms from two chelaling ligands. The P-Pd-P bond angles nearly match the idealized 109.5 degrees geometry expected for a d(10) metal center in a tetrahedral ligand field. The tetrahedral geometry of the metal center forces the alkyne termini separation of the enediyne ligand to a distance of 3.47 Angstrom, which results in a thermally stable compound at room temperature, However, at 115 degrees C 1 exhibits solvent-dependent reactivity. In sigma-fluorotoluene, 1 decomposes via ligand dissociation, while in sigma-dichlorobenzene, carbon-halide bond activation of solvent occurs leading to the oxidative addition product trans-Pd((2-chlorophenyl)diphenylphosphine)(2)Cl-2 and free (2-chlorophenyl)diphenylphosphine. The thermal reactivity of 1 is markedly more endothermic (44 kcal/mol) than that of the known Pd(dppeb)Cl-2 analogue (12.3 kcal/mol), The diminished reactivity can be attributed to two factors: the increased alkyne termini separation in 1 (3.47 vs 3.3 Angstrom) due to the metal-mandated tetrahedral geometry of the Pd(0) center, and the resistance of the Pd(0) to adopting a planar transition state geometry to promote Bergman cyclization. Overall this study demonstrates that metal binding can impose structural consequences upon the enediyne ligand governed by the oxidation state and corresponding ligand field geometry of the metal center.

  DOI：

  10.1021/ja9944094