10组复合物的金属对金属结合
Johann A Hlina1, James R Pankhurst1, Nikolas Kaltsoyannis2,3
1EaStCHEM School of Chemistry, University of Edinburgh , Joseph Black Building, The King's Buildings, Edinburgh EH9 3FJ, U.K.
Journal of the American Chemical Society
|March 5, 2016
概括
新的异金属复合体揭示了短的10组金属键. DFT计算和实验数据显示显著的U-M共价结合,U-Ni比U-Pd具有更高的结合顺序.
科学领域:
- 无机化学
- 有机金属化学
- 计算化学
背景情况:
- 具有和10组金属的异金属复合物对理解d-f块结合有兴趣.
- 之前的研究已经探讨了与金属的相互作用,
研究的目的:
- 合成和描述新型异金属10组金属复合物.
- 使用实验和计算方法研究金属 (U-M) 键的性质和强度.
- 将10组不同金属 (Ni,Pd,Pt) 的结合特性进行比较,并探索连接物替代的影响.
主要方法:
- 合成IU{IV}{OAr}{P}-κ{2}O,P{3}并随后与Ni{0},Pd{0}和Pt{0}进行反应.
- 使用可变温度NMR光谱学,电化学和单晶X射线衍射进行表征.
- 密度功能理论 (DFT) 的计算,包括自然人口分析 (NPA),自然局部分子轨道 (NLMO) 组成,以及原子在分子中的量子理论 (QTAIM) 分析.
主要成果:
- 已成功制备了具有短 U-M 键的异金属复合物,比之前报告的 d-f 块双金属更短.
- 实验和DFT数据显示U-Ni和U-Pd复合物的良好一致性.
- 分析表明5f和6d轨道在共价键中具有显著的参与,U-Ni键具有比U-Pd更大的移位指数 (键顺序).
- 与金属的结合强度从Ni降低到Pt,化物替代增强了与化物相比的结合强度.
- 尽管距离很短,但计算方法表明U-TM键次序较低,Pd的定位值轨道比Ni更多.
结论:
- 这项研究证明了异金属复合体中异常短的U-M键的形成.
- DFT和实验结果提供了这些U-M债券的共价性质和电子结构的见解.
- 这些发现有助于理解d-f块元素的粘合原理,并为设计新的基材料提供基础.
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