三坐标铁(IV) 双复合物与氨基碳素结合:合成,结构和反应性
Lei Wang1, Lianrui Hu2, Hezhong Zhang1
1State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , 345 Lingling Road, Shanghai 200032, P. R. China.
Journal of the American Chemical Society
|October 28, 2015
概括
合成和表征了新的铁复合物,揭示了脱和Si-H键激活中的独特反应性. 这些发现有助于我们更好地了解催化过程中的高价值铁中间体.
科学领域:
- 有机金属化学
- 催化剂
- 无机化学
背景情况:
- 在铁催化反应中,高价值铁化物是至关重要的但罕见的反应中间体.
- 了解它们的结构和反应性对于开发新的催化转换至关重要.
研究的目的:
- 合成和表征新的三坐标铁(IV) 双复合物.
- 研究这些复合体在关键化学转换中的反应性.
主要方法:
- 从铁的前体和有机酸盐中合成铁胺复合物.
- 使用NMR光谱,Mössbauer光谱和X射线衍射进行了表征.
- 反应性研究包括脱,Si-H键激活和循环添加反应.
- 使用密度函数理论 (DFT) 的计算分析.
主要成果:
- 成功合成和表征了四种具有低旋转单片基态的新铁 (IV) 复合物.
- 具有独特的反应性,包括分子内脱和Si-H键激活.
- 观察到 [2+2]-加法反应和组转移反应.
- DFT计算揭示了观察到的反应的机理性洞察力,突出了三重路径偏好.
结论:
- 铁的低坐标性和d(4) 电子数是其独特反应性的关键.
- 这些发现为设计具有挑战性的铁基催化剂提供了基础.
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