Understanding the Electronic Structure and Stability of BnXn0/2-(n=4,6;X =H,F,Cl,Br,I,At,Ts) Clusters

• 作者: Ruo-Ya Wang Jing-Xuan Zhang Xue-Lian Jiang Nana Ma Xuenian Chen Cong-Qiao Xu Jun Li
• 来源期刊: 中国化学（英文版）
• 年，卷（期）: 2021,（7）
• 所属期刊栏目: Concise Reports
• 页码范围: 1811-1818
• 页数: 8页
• 语种: 英文
• DOI: 10.1002/cjoc.202100072

摘要

Main observation and conclusion Borane clusters and their derivatives have attracted extensive attention in inorganic chemistry due to their fascinating multi-center bonding patterns and physicochemical properties.Here we report a systematic theoretical investigation on the geometry,electronic structur and chemical bonding of BnXn0/2-(n =4,6;X =H,F,Cl,Br,I,At,Ts) clusters,attempting to explore their bonding features,exceptional stability and the ligand effect.We find that the electronic structure and stability of BnXn0/2-clusters can be tuned by the size of the boron cage and electronegativity of the ligand.Fragment orbital energy matching and orbital overlap are of great im-portance to the covalency of the cluster.In addition to the ionic electrostatic interaction that dominates the bonding interaction and decreases as the ligand becomes heavier,multi-center bonding covalency determined by the orbital interaction increases accordingly,attributing to the reducing electronegativity.The σ-donations from the ligand to the boron cage as well as multi-center two-electron(nc-2e) bonding contribute to the σ aromaticity and superb stability.This work reveals the foremost factors that determine the struc-ture and stability of boron clusters,and provides insights into the nature of chemical bonding for species with boron cages and even bulk boron.