一个中间的 (IV) 化物复合物及其N-迁移的插入产物
Eva M Zolnhofer1, Martina Käß, Marat M Khusniyarov
1Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander University Erlangen - Nürnberg (FAU) , Egerlandstr. 1, 91058 Erlangen, Germany.
Journal of the American Chemical Society
|September 23, 2014
概括
低温实验揭示了一个高度反应性的 (IV) 化物种,由亚齐多复合物形成. 这种短暂的化物经历N-迁移的插入,产生一种罕见的,奇拉的,三角形的金字塔式合金 ((II) 复合体.
科学领域:
- 无机化学 无机化学
- 有机金属化学 有机金属化学
- 频谱学是一种光谱学.
背景情况:
- 研究低协调,高价值金属化物物种的反应性对于理解转移机制至关重要.
- 亚酸复合物作为生成反应性化物中间体的前体.
- 金属中心的电子配置和旋转状态决定了它们的反应性和稳定性.
研究的目的:
- 合成和描述一种高价值的化物种.
- 为了阐明化中间体的反应途径.
- 描述产生的N-迁移插入产品及其独特的结构特征.
主要方法:
- 亚酸复合物的低温 (10 K) 光解.
- 电子磁共振 (EPR) 光谱仪用于中间监测.
- 密度函数理论 (DFT) 对电子结构和反应路径的计算.
- 使用CHN元素分析,NMR,IR,UV-vis,SQUID磁力测量和X射线晶体学,对产品进行全面的表征.
主要成果:
- 在低温下从亚齐多前体 (1) 中形成一种高反应性,高价值的 (IV) 化物 (2) 种.
- DFT计算支持低旋转的d(5),S=1/2配置的二氧化.
- 隔离和表征的N-迁移插入产品,一个三角形金字塔的复合物 (3).
- 从化物 (2) 到产品 (3) 的反应途径通过容易的N-迁移插入,具有低激活屏障 (2.2 kcal mol(-1)).
结论:
- 该研究表明,产生和表征一种短暂的,高价值的 (IV) 化物种.
- (IV) 化物经历了易于N-迁移的插入到Co-C键中.
- 由此产生的 (II) 复合物 (3) 是一种罕见的,具有多种多样的捐赠体的性,三角形金字塔复合物的例子,突出显示了不寻常的协调化学.
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