硫铝桥键稳定平面CAl4结构的理论研究  

Theoretical Studies on Enhancing the Stability of the Planar CAl_4 by Al-S Bridge

作　　者：张醒醒 王艺桥 耿允[1] 张珉[1] 苏忠民[1] ZHANG Xingxing;WANG Yiqiao;GENG Yun;ZHANG Min;SU Zhongmin(Institute of Functional Material Chemistry,Faculty of Chemistry, Northeast Normal University,Changchun 130024,China)

机构地区：[1]东北师范大学化学学院,功能材料化学研究所,长春130024

出　　处：《高等学校化学学报》2018年第11期2485-2491,共7页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21673036);中央高校基本科研业务费(批准号:2412018ZD006);吉林省教育厅十三五项目资助.

摘　　要：在B3LYP/def2-TZVP水平下,利用硫铝桥连平面CAl_4结构,设计了含平面四配位碳的单硫桥连CAl_4S^-和具有准平面四配位碳的四硫桥连CAl_4S_4结构.团簇搜索结果表明两团簇均为势能面的极小值点,并且两团簇均具有双重芳香性(σ+π).单硫桥连CAl_4S得失电子的稳定性研究结果表明,CAl_4S^-为不同价态下的能量最低点,说明其热力学和动力学稳定性最好,证明其在实验中被捕获的可能性极大.准平面结构CAl_4S_4的适应性自然密度划分(AdNDP)分析表明,其稳定性主要来源于价电子的离域,其中三中心二电子σ键维持Al-S骨架的稳定,五中心二电子σ键维持C-Al核心的稳定,五中心二电子π键有利于整个准平面的整体稳定性.Two planar tetracoordinate carbon(pTC)derivatives,planar CAl 4S-and quasi-planar CAl 4S 4,were investigated to stabilize the planar CAl 4 core.It was indicated that through structural searches at the B3LYP/def2-TZVP level both of the proposed clusters by the Al-S bridge were global minima of potential energy surface with double aromaticity(σ+π).The planar CAl 4S-was likely to be captured in the experiment due to its thermodynamic stability.The adaptive natural density partitioning(AdNDP)analysis of quasi-planar CAl 4S 4 suggests that its stability was mainly contributed by partial delocalization of electrons.Four 3-center 2-electronσ-bonds maintain the stability of the Al-S framework;three 5-center 2-electronσ-bonds maintain the stability of the C-Al core;one 5-center 2-electronπ-bond facilitates the integral stability of the entire quasiplane.

关 键 词：平面碳 四配位碳 芳香性 密度泛函理论 化学键 

分 类 号：O641[理学—物理化学]