Influence of Molecular Structure on the Dimerization Reactivity of Germaaromatic Compounds： a Theoretical Study

• 作者: FANG De-Cai WANG Yan ZENG Xiao-Lan ZHANG Lu-Lu
• 来源期刊: 结构化学
• 学科: 化学
• 关键词: 二聚反应 分子结构 化合物 反应势能面 密度泛函理论 计算结果 异步方式 电子性质
• 年，卷（期）: 2012,（9）
• 页码范围: 1365-1372
• 页数: 8页
• 分类号: O623.124|O561.1
• 语种: 英文

摘要

Density functional theory （DFT） calculations, at the B3LYP/6-311G＊＊ level of theory, were performed to study the reaction mechanism and potenti4the potential energy surface of the studied reactions was investigated. Our calculation results show that [2 ＋ 2] and [4 ＋ 4] reactions are concerted and synchronous processes; while [4 ＋ 2] reactions proceed via a concerted but asynchronous way in general. [2 ＋ 2] and [4 ＋ 2] reactions of germabenzenes and 1-germana- phthalene proceed much more easily than the corresponding [4 ＋ 4] reaction, both thermo- dynamically and kinetically; while most [4 ＋ 2] paths have lower activation barrier than the corres- ponding [2 ＋ 2] ones. As the number of six-membered aromatic rings in reactant molecules becomes larger, [2 ＋ 2], [4 ＋ 2] and [4 ＋ 4] reactions become easier to proceed. The influence of substituents at the Ge atom of germabenzenes on the potential energy surface of [2 ＋ 2] and [4 ＋ 2] reactions correlates with their electronic properties and volume. Solvent effect is not crucial for the potential energy surfaces of the studied reactions.