【摘要】 使用密度泛函理论的B3LYP方法,对氧气与具有d0电子组态的W过渡金属有机化合物(CH3)2W(CH2)2的反应进行了研究,探讨了(CH3)2W(CH2)2与氧气反应的反应机理.确定了反应物、中间体、产物和过渡态的几何构型和反应势垒,讨论了反应过程中几何构型以及电子自旋密度的变化.化学反应式显示,d0电子组态的过渡金属有机化合物(CH3)2W(CH2)2与氧气的反应的净结果是氧分子氧化WCH2双键.反应过程中电子自旋密度变化的分析揭示了氧气对(CH3)2W(CH2)2中双键的氧化实质上以氧分子上的未成对电子向金属的空d轨道转移为前提.更多还原

【Abstract】 The theoretical study on the mechanism of oxygen molecule reaction with the organometallic complex Me2W(CH2)2, where Me2W(CH2)2 possesses the d0 electronic configuration for the metal center, was carried out with the density functional theory B3LYP method. The optimal structures of the reactant, the singlet and the triplet intermediates, the singlet and the triplet transition states, and the product were located. The electron spin densities of the triplet systems and the reaction barriers were obtained. Calculation results indicate that the unpaired electrons in oxygen molecule and the unoccupied d orbit of the metal center play an important role in the reaction of Me2W(CH2)2 with oxygen molecule. It is the unpaired electron transferring from oxygen molecule to the metal center of the organometallic complex Me2W(CH2)2 that invokes the formation of the product Me2W(O)(CH2).更多还原