(Py₃CH)Pd^II([1,1'-biphenyl]-2-yl)(I) | 1431223-01-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: (Py₃CH)Pd^II([1,1'-biphenyl]-2-yl)(I)
• 英文别名: 2-(Dipyridin-2-ylmethyl)pyridine;palladium(2+);phenylbenzene;iodide
• CAS: 1431223-01-6
• 化学式: C₂₈H₂₂IN₃Pd
• 分子量: 633.827
• InChiKey: NIEVASNSWDTEDX-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  3.21
• 重原子数：
  33
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (Py₃CH)Pd^II([1,1'-biphenyl]-2-yl)(I) 以 二氯甲烷 、 氯仿 、 水 为溶剂， 反应 0.16h， 生成 [(Py3CH)PdIV([1,1'-biphenyl]-2-yl)(Br)2][OTf]
  参考文献：
  名称：

  A Detailed Study of Acetate-Assisted C–H Activation at Palladium(IV) Centers

  摘要：

  This report describes a detailed investigation of acetate-assisted C-H activation at Pd-IV centers supported by the tris(2-pyridyl)-methane (Py3CH) ligand. Mechanistic information about this transformation has been obtained through the following:, (i) extensive one- and two-dimensional NMR analysis, (ii) reactivity studies of a series of substituted analogues, and (iii) isotope effect studies. These experiments all suggest that C-H activation at [(Py3CH)Pd-IV(biphenyl)Cl-2)(+) occurs via a multistep process involving chloride-to-acetate ligand exchange followed by conformational and configurational isomerization and then C-H cleavage. The data also suggest that C-H cleavage proceeds via an acetate-assisted mechanism with the carboxylate likely serving as an intramolecular base. The viability of acetate-assisted C-H activation at high valent palladium has important implications for the design and optimization of catalytic processes involving this transformation as a key step.

  DOI：

  10.1021/ja401557m
• 作为产物：
  描述：

  2-氟吡啶 在 4-叔丁基吡啶 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 4.33h， 生成 (Py₃CH)Pd^II([1,1'-biphenyl]-2-yl)(I)
  参考文献：
  名称：

  A Detailed Study of Acetate-Assisted C–H Activation at Palladium(IV) Centers

  摘要：

  This report describes a detailed investigation of acetate-assisted C-H activation at Pd-IV centers supported by the tris(2-pyridyl)-methane (Py3CH) ligand. Mechanistic information about this transformation has been obtained through the following:, (i) extensive one- and two-dimensional NMR analysis, (ii) reactivity studies of a series of substituted analogues, and (iii) isotope effect studies. These experiments all suggest that C-H activation at [(Py3CH)Pd-IV(biphenyl)Cl-2)(+) occurs via a multistep process involving chloride-to-acetate ligand exchange followed by conformational and configurational isomerization and then C-H cleavage. The data also suggest that C-H cleavage proceeds via an acetate-assisted mechanism with the carboxylate likely serving as an intramolecular base. The viability of acetate-assisted C-H activation at high valent palladium has important implications for the design and optimization of catalytic processes involving this transformation as a key step.

  DOI：

  10.1021/ja401557m