比斯皮丁-铁(IV) -托西利米多物种的合成,特征和反应性
Thomas Josephy1, Ravi Kumar2, Katharina Bleher1,3
1Anorganisch-Chemisches Institut, Universität Heidelberg, INF 270,Heidelberg D-69120, Germany.
Inorganic chemistry
|June 14, 2024
概括
合成和研究了铁(IV) - - 托西利米多复合物与双胺配体. 这些铁复合体表现出中间自旋状态,研究了它们在C-H激活和原子转移反应中的反应性,揭示了固态效应影响氧与原子转移速率.
科学领域:
- 无机化学 无机化学
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
背景情况:
- 铁复合物与氨基/皮里丁连接体在氧化催化过程中至关重要.
- 五牙联体为金属中心提供独特的协调环境.
- 了解铁 (IV) - imido和铁 (IV) - oxo物种是阐明催化机制的关键.
研究的目的:
- 通过同位素双酸连接物合成和表征新的铁(IV) - 托西利米多复合物.
- 研究这些复合物的电子特性和反应性作为氧化剂.
- 在原子转移反应中比较铁 (IV) -托西利米多和铁 (IV) -氧合物复合物的活性.
主要方法:
- 铁 (IV) - 托西利米多复合物的合成与五酸双酸连接物.
- 使用UV对NIR,Mössbauer光谱和HR-ESI-MS进行了表征.
- 涉及C-H激活和原子转移到离子的活性研究.
- 密度功能理论 (DFT) 分析以探测反应机制.
主要成果:
- 两种具有中间旋转 (S=1) 的新铁(IV) -托西利米多复合物成功合成和表征.
- 反应性研究表明了C-H激活和原子转移能力.
- 氧原子转移通常比原子转移更快,除了固态阻碍起作用的特定配体外.
结论:
- 这项研究扩展了铁(IV) - 托西利米多复合体的系列,具有多样化的连接体支架.
- 固态效应,特别是胺丰富的配体,显著影响氧与原子转移的相对速率.
- DFT分析提供了对控制这些铁氧化剂反应性的电子和硬质因素的见解.
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