在选择的储物材料中化物-化物相互作用的理论描述
Aleksandra L Ptaszek1, Filip Sagan1, Radosław Filas1
1Faculty of Chemistry, Jagiellonian University, ul. Gronostajowa 2, 30-387, Krakow, Poland.
金属化物可以形成有吸引力的化物-化物相互作用 (Hδ-⋅⋅⋅δ-H),比键更强. 连接物选择显著影响相互作用强度,素连接物增强过渡金属复合物的稳定性.
科学领域:
- 无机化学 无机化学
- 计算化学计算化学
- 材料科学 材料科学 材料科学
背景情况:
- 对金属化物作为富含的来源越来越感兴趣.
- 化物-化物接触 (Hδ-⋅⋅⋅δ-H) 对形成的相关性.
- 缺乏关于H相互作用的性质 (吸引力与排斥性) 的共识.
研究的目的:
- 阐明控制同极化物 - 化物相互作用的物理因素 (Hδ-⋅⋅⋅δ-H).
- 在过渡金属复合体中研究这些相互作用 (HCoL,L=CO,PPh,PH).
主要方法:
- 使用化学价值的自然轨道进行能量分解分析的应用 (ETS-NOCV).
- 使用交互量子原子 (IQA) 和非共价相互作用 (NCI) 的计算.
- 采用密度函数理论 (DFT) 和相关的方法,用于结合引数 (L4CoH⋅⋅⋅HCoL4).
主要成果:
- 证明了化物-化物相互作用可以具有吸引力,并且比键更强.
- 添加物的稳定性随着素连接体的安装而增加 (CO≪PPh3~PH3).
- H−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
结论:
- 二原子化物-化物相互作用 (CoH⋅⋅⋅HCo) 呈现着类似黑的行为,在某些配置中具有吸引力,在其他配置中具有排斥力.
- 侧碳酸连接物通过共价脱和库伦比贡献稳定H-δ-⋅⋅⋅δ-H结合结构.
- 用氨酸连接体挤满的系统通过 π⋅⋅⋅π 堆叠和 C-H⋅⋅⋅π 相互作用进一步稳定.
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