在Pd催化多米诺反应中,在Pd (II) 中心或Pd (IV) 中介物之间转移
Diego J Cárdenas1, Belén Martín-Matute, Antonio M Echavarren
1Departamento de Química Organica, Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain. diego.cardenas@uam.es
Journal of the American Chemical Society
|April 13, 2006
概括
这项研究使用了计算方法来探索催化多米诺反应. 结果表明 (II) 复合物,而不是 (IV) 中间体,是形成新碳-碳键的关键.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 计算化学的计算化学
背景情况:
- 催化反应对于形成碳-碳键至关重要.
- 了解反应机制对于催化剂设计和优化至关重要.
研究的目的:
- 阐明Pd催化多米诺反应形成C(sp2) -C(sp2) 键的机制.
- 为了比较两个拟议的反应途径的可行性.
主要方法:
- 使用密度函数理论 (DFT) 的计算.
- 研究了含有素 (PH3) 和水 (H2O) 连接体的模型复合体.
- 还研究了替代辅助配体 (形式胺) 和烯化 (丁,乙烯).
主要成果:
- 对Pd(0) 前体的氧化添加乙烯比对Pd(II) 形循环更有利.
- 在Pd(II) 复合体之间发生的转金属反应很容易.
- 同样的趋势也被观察到与酸和formamide配体.
结论:
- 帕拉 (II) 的中间体和转基因传递通路是最受欢迎的.
- (IV) 的中间体不太可能参与这些特定的多米诺反应.
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