超酸中四重甲酸盐的四倍质子化:固态中的和π-孔结合
Tim-Niclas Streit1, Malte Sellin2, Susanne M Rupf1
1Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstraße 34-36, 14195 Berlin, Germany.
Inorganic chemistry
|December 29, 2025
概括
通过使用超酸来合成,,白金和黄金的新异化物复合物. 这些复合物表现出独特的金属-相互作用,称为区域结合,挑战它们的典型化学行为.
科学领域:
- 协调化学 协调化学
- 超分子化学 超分子化学
- 计算化学的计算化学
背景情况:
- 第10组金属四甲酸盐 (M = Ni,Pd,Pt) 和四甲酸盐 (Au) 是典型的核爱型正方形平面复合体.
- 像HF/SbF5这样的超酸是强大的试剂,能够产生质子联体并改变复杂的结构.
- 了解分子间相互作用对于设计新材料和预测化学反应性至关重要.
研究的目的:
- 为了合成和结构性地表征新的同质性异酸复合体.
- 研究这些新复合体中的分子间相互作用的性质,包括M··F接触.
- 用计算方法阐明金属中心的电子特性和粘合特性.
主要方法:
- K2[MII[CN]4]和K[AuIII[CN]4]与HF/SbF5.5.4发生反应
- 单晶X射线衍射用于结构特征.
- 密度函数理论 (DFT) 的计算,包括MEP,QTAIM和NBO分析.
主要成果:
- 均性异酸复合物的形成:[MII(CNH) [4][SbF6]2 (M = Ni, Pd, Pt) 和[AuIII(CNH) [4][SbF6]3·2HF. 在这种情况下,
- 观察强大的H···F结网络和较弱的F···N接触.
- 在范德瓦尔斯半径以下的M···F接触的识别,称为区域结合.
- DFT计算证实了金属中心上的电友π孔以及M··F相互作用的非共价性.
结论:
- 与超酸的反应将典型的核友金属中心转化为电友金属中心,由π孔形成证明.
- 区域结合 (M··F接触) 在这些复合体中代表了显著的分子间相互作用.
- 计算分析提供了对这些新异化物复合物的电子结构和结合的详细了解.
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