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两性离子碱金属甲烷化物、硅化物和锗化物的电子性质——实验与计算相结合的方法

Electronic nature of zwitterionic alkali metal methanides, silanides and germanides - a combined experimental and computational approach.

作者信息

Li H, Aquino A J A, Cordes D B, Hase W L, Krempner C

机构信息

Texas Tech University , Department of Chemistry and Biochemistry , Box 41061 , Lubbock , Texas 79409-1061 , USA . Email:

出版信息

Chem Sci. 2017 Feb 1;8(2):1316-1328. doi: 10.1039/c6sc02390h. Epub 2016 Oct 7.

DOI:10.1039/c6sc02390h
PMID:28451273
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5360169/
Abstract

Zwitterionic group 14 complexes of the alkali metals of formula [C(SiMeOCHCHOMe)M], (M-), [Si(SiMeOCHCHOMe)M], (M-), [Ge(SiMeOCHCHOMe)M], (M-), where M = Li, Na or K, have been prepared, structurally characterized and their electronic nature was investigated by computational methods. Zwitterions M- and M- were synthesized reactions of [Si(SiMeOCHCHOMe)] () and [Ge(SiMeOCHCHOMe)] () with MOBu (M = Li, Na or K), resp., in almost quantitative yields, while M- were prepared from deprotonation of [HC(SiMeOCHCHOMe)] () with LiBu , NaCHPh and KCHPh, resp. X-ray crystallographic studies and DFT calculations in the gas-phase, including calculations of the NPA charges confirm the zwitterionic nature of these compounds, with the alkali metal cations being rigidly locked and charge separated from the anion by the internal OCHCHOMe donor groups. Natural bond orbital (NBO) analysis and the second order perturbation theory analysis of the NBOs reveal significant hyperconjugative interactions in M--M-, primarily between the lone pair and the antibonding Si-O orbitals, the extent of which decreases in the order M- > M- > M-. The experimental basicities and the calculated gas-phase basicities of M--M- reveal the zwitterionic alkali metal methanides M- to be significantly stronger bases than the analogous silanides M- and germanium M-.

摘要

已制备出通式为[C(SiMeOCHCHOMe)M]⁻、[Si(SiMeOCHCHOMe)M]⁻、[Ge(SiMeOCHCHOMe)M]⁻（其中M = Li、Na或K）的碱金属两性离子14族配合物，对其进行了结构表征，并通过计算方法研究了它们的电子性质。两性离子M⁻和M⁻分别通过[Si(SiMeOCHCHOMe)]²⁻和[Ge(SiMeOCHCHOMe)]²⁻与MOBu（M = Li、Na或K）反应合成，产率几乎定量，而M⁻分别由[HC(SiMeOCHCHOMe)]²⁻用LiBu、NaCHPh和KCHPh去质子化制备。气相中的X射线晶体学研究和密度泛函理论计算，包括NPA电荷计算，证实了这些化合物的两性离子性质，碱金属阳离子被刚性锁定，电荷通过内部的OCHCHOMe供体基团与阴离子分离。自然键轨道（NBO）分析和NBO的二阶微扰理论分析揭示了M⁻ - M⁻中存在显著的超共轭相互作用，主要是孤对电子与反键Si - O轨道之间的相互作用，其程度按M⁻ > M⁻ > M⁻的顺序降低。M⁻ - M⁻的实验碱性和计算得到的气相碱性表明，两性离子碱金属甲烷化物M⁻比类似的硅化物M⁻和锗化物M⁻碱性要强得多。

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