低坐标双氨酸和单氨酸Ni(0) 复合物:C-S交叉合中的合成和反应性
M Trinidad Martín1, Carlos J Carrasco1, Nazaret Santamaría1
1Departamento de Química Inorgánica, Universidad de Sevilla, 41012 Sevilla, Spain. mnicasio@us.es.
Dalton transactions (Cambridge, England : 2003)
|January 9, 2025
概括
预制的 (((0) 复合物与重的单素联体有效催化C-S交叉合反应. 这些Ni(0) 前催化剂与Ni(II) 相比具有更高的反应性,可以在温和条件下进行具有挑战性的合.
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.
- 合成化学 合成化学
背景情况:
- 预制的Ni(0) 复合物在交叉合反应中未被充分利用为预催化剂.
- 低坐标Ni(0) 复合物提供了活性物种的直接结合.
- 大量的素配体对于稳定反应性物种至关重要.
研究的目的:
- 准备和评估由重的单氨酸连接体支持的低坐标Ni(0) 复合体.
- 研究这些Ni(0) 复合体在C-S交叉合反应中的催化应用.
- 为了比较Ni(0) 和Ni(II) 预催化剂与相似的连接体环境的反应性.
主要方法:
- 合成两个家族的Ni(0) 复合物:双氨酸添加物[Ni(PR2Ar') ]和单氨酸衍生物[Ni(PR2Ar') ].
- 密度函数理论 (DFT) 计算来理解复杂的结构.
- 在C-S交叉合反应中进行催化试验,包括挑战化和基合物.
主要成果:
- 单氨酸Ni(0) 复合物比双氨酸Ni(0) 添加物具有更高的催化活性.
- Ni(0) 前催化剂表现出比具有相同素连接体的 Ni(II) 前催化剂更高的反应性.
- 使用低催化剂负载 (1-5mol%) 的化与基醇的成功合.
结论:
- 单氨酸Ni(0) 复合物有助于产生高度反应的单化Ni(0) 物种.
- 与Ni(II) 前催化剂相比,Ni(0) 前催化剂提供了更容易的激活途径.
- 开发的Ni(0) 前催化剂在温和条件下实现高效且具有挑战性的C-S交叉合反应.
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