bis(1,2-bis(diphenylphosphinoethynyl)benzene)palladium(0) | 265114-75-8

• 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(1,2-bis(diphenylphosphinoethynyl)benzene)palladium(0)
• 英文别名: Pd(dppeb)2；Pd(1,2-bis(diphenylphosphinoethynyl)benzene)2；Pd(dppeb)；2-[2-(2-Diphenylphosphanylethynyl)phenyl]ethynyl-diphenylphosphane;palladium
• CAS: 265114-75-8
• 化学式: C₆₈H₄₈P₄Pd
• 分子量: 1095.44
• InChiKey: HQWQRXHALXXQAT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.14
• 重原子数：
  73
• 可旋转键数：
  16
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  bis(1,2-bis(diphenylphosphinoethynyl)benzene)palladium(0) 在 cyclohexadiene 作用下， 以 further solvent(s) 为溶剂， 生成 钯
  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
• 作为产物：
  描述：

  1,2-bis(diphenylphosphinoethynyl)benzene 、 bis-triphenylphosphine-palladium(II) chloride 在 肼 作用下， 以 苯 为溶剂， 反应 16.0h， 生成 bis(1,2-bis(diphenylphosphinoethynyl)benzene)palladium(0)
  参考文献：
  名称：

  Compounds, composition, and methods for photodynamic therapy

  摘要：

  揭示了一种在光动力疗法中特别有用的新化合物、组合物和方法。具体来说，这些创新化合物、组合物和方法涉及在光的存在下形成细胞毒性自由基物质。值得注意的是，本发明的化合物、组合物和方法在光动力疗法中不需要氧气的存在，因此依赖于产生自由基的单分子机制。这些创新的化合物、组合物和方法可以用于治疗癌症以及由原生动物、真菌、细菌和病毒引起的感染。

  公开号：

  US06828439B1

文献信息

• Structure and Thermal Reactivity of a Novel Pd(0) Metalloenediyne
  作者：Nicole L. Coalter、Thomas E. Concolino、William E. Streib、Chris G. Hughes、Arnold L. Rheingold、Jeffrey M. Zaleski

  DOI：10.1021/ja9944094

  日期：2000.4.1

  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.
• Compounds, composition, and methods for photodynamic therapy
  申请人：Advanced Research and Technology Institute, Inc.

  公开号：US06828439B1

  公开（公告）日：2004-12-07

  Disclosed are novel compounds, compositions, and methods that are particularly useful in photodynamic therapy. In particular, the inventive compounds, compositions, and methods relate to the formation of cytotoxic radical species in the presence of light. Significantly, the compounds, compositions, and methods of the present invention do not require the presence of oxygen in the photodynamic therapy and, as such, rely on a unimolecular mechanism for producing the radicals. The inventive compounds, compositions, and methods can be used, for example, in the treatment of cancers as well as infections caused by microorganisms such as protozoa, fungi, bacteria, and viruses.

  揭示了一种在光动力疗法中特别有用的新化合物、组合物和方法。具体来说，这些创新化合物、组合物和方法涉及在光的存在下形成细胞毒性自由基物质。值得注意的是，本发明的化合物、组合物和方法在光动力疗法中不需要氧气的存在，因此依赖于产生自由基的单分子机制。这些创新的化合物、组合物和方法可以用于治疗癌症以及由原生动物、真菌、细菌和病毒引起的感染。