重碱土金属元素d轨道参与形成化学键

doi:10.12461/PKU.DXHX202604013

摘要/Abstract

摘要： 作为典型的主族元素，碱土金属通常是以+II价的经典形式存在于化合物中。但是近年来低氧化价态主族化学引起了人们的兴趣。人们发现了一系列含有低价态(0和+I价)的较轻的碱土金属(Be和Mg)的奇异化合物。但是由于较重的碱土金属具有较低的第二电离能，类似的化合物鲜有报道。本文概述了近年来在低温基质和超声分子束中的重碱土金属(Ca，Sr和Ba)化学的光谱学研究，发现这些金属可以形成具有类似过渡金属的具有18个价电子结构的饱和配合物，理论分析表明重碱土金属较低的(n-1) d轨道能量对这些物种的形成起了决定性作用。该系列研究表明重碱土金属具有类过渡金属的性质，加深了对元素周期表和元素周期律的理解，为结构化学、合成化学和催化化学提供了新的启发和思路。

关键词: 碱土金属, d轨道, 过渡金属, 18电子规则, 主族元素

Abstract: As typical main-group elements, alkaline earth metals predominantly exist in compounds with their characteristic +II oxidation state. Recent advances in low-valent main-group chemistry have generated significant interest and resulted in numerous unusual compounds containing beryllium and magnesium in low oxidation states (0 and +I). However, analogous compounds of heavier alkaline earth metals remain scarce due to their diminished second ionization energies. This review summarizes and discusses recent spectroscopic investigations of heavy alkaline earth metals (Ca, Sr, and Ba) in cryogenic matrices and supersonic molecular beams, emphasizing their ability to form 18-electron saturated complexes resembling those of transition metals. Theoretical analyses reveal that the relatively low energy of (n-1) d orbitals in heavy alkaline earth metals significantly promotes the formation of such species. These findings collectively establish the transition-metal-like characteristics of heavy alkaline earth metals, advancing our comprehension of periodic trends and offering novel perspectives for structural chemistry, syntheticchemistry, and catalysis.

Key words: Alkaline earth metal, d Orbitals, Transitional metal, 18-Electron rule, Main group element

王冠军, 金佳晔, 李传坤. 重碱土金属元素d轨道参与形成化学键[J]. 大学化学, 2026, (): 2604013.

Guanjun Wang, Jiaye Jin, Chuankun Li. The role of d orbitals in heavy alkaline earth metal chemical bonding[J]. University Chemistry, 2026, (): 2604013.

链接本文: https://www.dxhx.pku.edu.cn/CN/10.12461/PKU.DXHX202604013

https://www.dxhx.pku.edu.cn/CN/Y2026/V/I/2604013

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