从稀土-丁烯复合物中氧化物的合和释放
Arun Kumar Bar1, María José Heras Ojea1, Jinkui Tang2
1Department of Chemistry, School of Life Sciences, University of Sussex, Brighton BN1 9QJ, U.K.
Journal of the American Chemical Society
|February 18, 2020
概括
易斯酸性金属复合物与丁烯复合物 (DNIC) 反应形成新的桥梁结构. 在DNIC上大量的替代剂会触发异常的NO联接,并从单个铁中心释放N2O.
科学领域:
- 有机金属化学
- 无机化学
- 协调化学
背景情况:
- 丁烯复合物 (DNIC) 在各种化学和生物过程中具有重要作用.
- DNIC与易斯酸的反应性尚未完全理解.
- 稀土元素具有独特的协调特性.
研究的目的:
- 研究易斯酸[Cp*2M]+ (M = Y,Gd) 与丁烯复合物的反应.
- 探索异基桥接DNIC的形成及其随后的反应性.
- 阐明影响NO联结和N2O释放的因素.
主要方法:
- 合成和描述异基桥接DNIC.
- 用光谱分析 (例如NMR,IR) 来确认结构.
- 在不同的条件下对反应性的研究,包括不同的替代剂 (Ar).
主要成果:
- 达到了与异基桥接的DNICs (Cp*) 2M (μ-ON) 2Fe (NacNacAr) 的形成.
- 当Ar=2,6-二甲时,可以观察到NO联结和N2O释放.
- 稀土金属的氧性和替代物的硬质量被确定为关键因素.
结论:
- 这项研究揭示了DNIC的新型反应模式,涉及NO合和N2O消除.
- 稀土金属的易斯酸促进同位素结合的形成,使NO配体接近.
- 在DNIC上的体替代物压力可以克服NO合的激活障碍,从而从单个铁中心释放N2O.
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