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碳族元素键的起源与性质。

Origins and properties of the tetrel bond.

作者信息

Scheiner Steve

机构信息

Department of Chemistry and Biochemistry, Utah State University, Logan, Utah 84322-0300, USA.

出版信息

Phys Chem Chem Phys. 2021 Mar 18;23(10):5702-5717. doi: 10.1039/d1cp00242b.

Abstract

The tetrel bond (TB) recruits an element drawn from the C, Si, Ge, Sn, Pb family as electron acceptor in an interaction with a partner Lewis base. The underlying principles that explain this attractive interaction are described in terms of occupied and vacant orbitals, total electron density, and electrostatic potential. These principles facilitate a delineation of the factors that feed into a strong TB. The geometric deformation that occurs within the tetrel-bearing Lewis acid monomer is a particularly important issue, with both primary and secondary effects. As a first-row atom of low polarizability, C is a reluctant participant in TBs, but its preponderance in organic and biochemistry make it extremely important that its potential in this regard be thoroughly understood. The IR and NMR manifestations of tetrel bonding are explored as spectroscopy offers a bridge to experimental examination of this phenomenon. In addition to the most common σ-hole type TBs, discussion is provided of π-hole interactions which are a result of a common alternate covalent bonding pattern of tetrel atoms.

摘要

四元键(TB)在与伙伴路易斯碱的相互作用中,会引入碳(C)、硅(Si)、锗(Ge)、锡(Sn)、铅(Pb)族元素作为电子受体。解释这种吸引相互作用的基本原理是根据占据轨道和空轨道、总电子密度以及静电势来描述的。这些原理有助于描绘出构成强四元键的因素。含四元元素的路易斯酸单体内部发生的几何变形是一个特别重要的问题,存在一级和二级效应。作为低极化率的第一周期原子,碳是四元键中不太愿意参与的元素,但它在有机化学和生物化学中的优势使得彻底了解其在这方面的潜力极为重要。由于光谱学为该现象的实验研究提供了桥梁,因此对四元键的红外和核磁共振表现进行了探索。除了最常见的σ-空穴型四元键外,还讨论了π-空穴相互作用,这是四元原子常见的交替共价键模式的结果。

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