化 Umpolung 通过氧化位置调节
Diego Martelino1, Samyadeb Mahato1, Warren VandeVen1
1Department of Chemistry, Simon Fraser University, Burnaby, British Columbia V5A 1S6, Canada.
Journal of the American Chemical Society
|June 24, 2022
概括
化物复合物的氧化表明,金属基氧化到Cr (VI) 导致umpolung,将终端化物的反应性从核爱性转变为电爱性. 基于基的氧化保持了核友性,突出了氧化位点对反应性的影响.
科学领域:
- 无机化学
- 有机金属化学
- 反应机制
背景情况:
- 酸盐复合物 (CrNSal) 的反应性正在研究中.
- 了解氧化位置 (金属与配体) 对于预测反应性至关重要.
- 副酸替代剂调节了联体的电子捐赠能力.
研究的目的:
- 为了研究Cr (V) 酸盐复合物的氧化.
- 确定氧化场所如何影响化物反应.
- 为了比较Cr (VI) 和Cr (V) 化物衍生物的反应性.
主要方法:
- 氧化Cr (V) 盐复合物与不同类型的替代物.
- 光谱和计算分析 (NPA电荷,MO能量).
- 使用B(C6F5) 3和PPh3进行反应性研究.
主要成果:
- 一个电子的氧化产生Cr (VI) 化物或Cr (V) 化物基,取决于替代剂.
- 与Mn类似物相比,Cr (VI) 衍生物具有减弱的化物同.
- (V) 连接基衍生物以核友性反应,而 (VI) 衍生物以电友性反应.
结论:
- 氧化位点决定了反应性:金属氧化到Cr (VI) 会导致化.
- 基于基的氧化保持了核友反应性.
- 在金属和配体氧化过程中,{CrN}单元的电子变化显著不同.
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