含有金属的碳酸结合物 的情况 (II) 与基于Se/Te的σ-洞供体的相互作用
Anton V Rozhkov1, Eugene A Katlenok1, Margarita V Zhmykhova1
1Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 7/9, 199034 Saint Petersburg, Russian Federation.
Journal of the American Chemical Society
|September 16, 2021
概括
这项研究探讨了 (II) 复合物和捐赠体之间的金属结. 这些通过DFT计算量化的相互作用揭示了独特的结合模式和不同的强度,影响了晶体结构和溶液的结合.
科学领域:
- 无机化学
- 超分子化学
- 晶体学
- 计算化学
背景情况:
- 具有核友金属中心的 (II) 复合物对非共价相互作用具有兴趣.
- 例如 (4-NC5F4) 2Ch,它们具有独特的结合能力.
- 了解金属配体相互作用对于设计新材料和催化剂至关重要.
研究的目的:
- 合成和表征 ((II) 复合物与基键捐赠者.
- 研究涉及金属的基键的性质和强度 (Ch·d2-PtII).
- 探索这些复合物的结构和溶液相关联.
主要方法:
- (II) 复合物的联合结晶 ([Pt ((ppy)) ((acac)) 和[Pt ((ppy)) ((tmhd)))) 与石化物捐赠体.
- 结果的共晶体的X射线衍射分析.
- 密度函数理论 (DFT) 计算 (PBE0-D3BJ) 来确定相互作用能量.
- 溶液状态NMR光谱 (1H,13C,19F,195Pt,125Te,HOESY,扩散NMR) 和同热定位热量计.
主要成果:
- 形成具有定义的包含金属的基键 (Ch·d2-PtII) 的同结构共晶体,能量范围为-7至-12 kcal/mol.
- 在一个共晶体中识别了三中心二叉相互作用,在另一个中识别了纯二中心,更强的素键.
- 通过光谱和热量计方法确认[Pt(ppy) ((tmhd) ]与溶液中的 (4-NC5F4) 2Te之间的1:1关联.
结论:
- 这项研究证明了涉及金属的基键的形成和特征.
- 这些键的强度和几何结构受复合物和素供体的影响.
- 这些发现为涉及和素的非共价相互作用提供了洞察力,这与材料科学有关.
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