一种低旋转的d5铁胺基:通过低坐标铁的烯捕获 (I) 提供了4坐标Fe (III) 复合物[PhB (CH2PPh2) 3]Fe=N-p-tolyl
Steven D Brown1, Theodore A Betley, Jonas C Peters
1Division of Chemistry and Chemical Engineering, Arnold and Mabel Beckman Laboratories of Chemical Synthesis, California Institute of Technology, Pasadena, California 91125, USA.
Journal of the American Chemical Society
|January 9, 2003
概括
研究人员合成了一种罕见的伪四面体铁 (I) 复合物[PhBP3]Fe (PPh3),该复合物氧化形成第一个单核铁 (III) 胺基[PhBP3]FeNAr. 这种胺基进一步与一氧化碳发生反应,产生二碳类物种.
科学领域:
- 有机金属化学 有机金属化学
- 铁复合体 铁复合体 铁复合体
- 协调化学 协调化学
背景情况:
- 低价值铁复合物的合成和表征对于理解铁的反应性至关重要.
- 单核铁胺化合物复合物很少见,它们的电子结构具有显著的兴趣.
- 铁复合物与化物和一氧化碳的反应性在催化和合成中是至关重要的.
研究的目的:
- 合成和表征一种新的伪四面体铁 (I) 复合物与[PhBP3]连接体.
- 为了研究铁(I) 复合物的氧化与酸,以形成铁胺基.
- 为了探索由此产生的铁化物与一氧化碳的反应性.
主要方法:
- [PhBP3]Fe(PPh3) 复合物的合成.
- 与酸发生氧化反应,形成铁胺复合物[PhBP3]FeNAr.
- 铁胺与一氧化碳的反应产生[PhBP3]Fe(CO) 2.2.
主要成果:
- 合成了一种罕见的伪四面体铁 (I) 复合体,[PhBP3]Fe (PPh3),具有S = 3/2基本状态.
- 铁 (I) 复合物被亚利酸迅速氧化,产生d5铁 (III) 胺基[PhBP3]FeNAr.
- 铁胺是低旋转的,是第一个单核铁胺,与二氧化碳反应释放异酸盐和[PhBP3]Fe胺CO) 2.
结论:
- 该研究报告了独特的铁I) 复合物的成功合成及其随后的转化为第一个单核铁III) imide.
- 铁胺基与二氧化碳的反应性表明了异酸盐释放和二乙烯基物种形成的新途径.
- 这些发现扩大了对铁的协调化学和新型铁和铁碳键的合成的理解.
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