逆转影响和- σ-结合驱动分子几何学:从硬到软的连接物修饰将氧化物从轴向转向赤道
Benedikt Kestel1, Daniel Pividori1, Sabyasachi Roy Chowdhury2,3
1Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Egerlandstrasse 1, Erlangen 91058, Germany.
Journal of the American Chemical Society
|July 23, 2025
概括
这项研究呈现了一种罕见的 (V) 氧复合物与赤道氧联体,由硫基联体稳定. 这与相关的氧联体复合物形成鲜明对比,并揭示了f元素化学中的新设计原理.
科学领域:
- 有机金属化学
- 无机化学
- 化学
背景情况:
- 在f元素化学中,终端氧复合物至关重要.
- 氧联体的协调部位 (轴与赤道) 显著影响复杂性质和反应性.
- 之前的研究主要涉及复合体中的轴性氧联体.
研究的目的:
- 合成和表征一种具有赤道氧联体的新型 (V) 氧复合物.
- 研究基于硫的配体对氧复合物的协调几何和电子结构的影响.
- 探索连接剂环境对氧物种反应性的影响.
主要方法:
- (III) 和 (V) 复合物的合成,使用基三酸盐和三酸盐连接物.
- 通过单晶X射线衍射,UV/VIS/NIR电子吸收,EPR光谱和SQUID磁力测量进行表征.
- 计算研究包括密度函数理论 (DFT) 和CASPT2计算,以合理化结构和电子差异.
主要成果:
- 一种罕见的赤道结合的终端 ((V) oxo复合物, (mes ((Me,AdArS) 3) UV(Oeq)
- 复合体2表现出CS对称性和U(V) 氧化状态,与其三相似的轴性氧联体形成鲜明对比.
- 量子化学计算显示,由于硫3p轨道与5f轨道的相互作用,酸盐复合物中存在稳定反向转变影响 (ITI).
结论:
- 结合一个tris-thiophenolate连接体提供了一个新的设计策略来稳定赤道结合的U ((V) oxo中心.
- 酸盐和酸盐复合物之间观察到的几何差异是由竞争的ITI和U-arene相互作用驱动的.
- 不同的协调模式和电子结构导致了差异化的反应性,只有酸盐类型激活H2O.
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