Theoretical Study on Mechanism of Cycloadditional Reaction Between Dichloro-Germylidene and Formaldehyde

用MP2/6-31G^*方法研究了单线态二氯亚甲基锗烯与甲醛环加成反应的反应机理,该反应有两条相互竞争的主反应通道,同时伴随着两中间体(INT3和INT4)副产物的生成. 第一条主反应通道所生成的物种为三员环中间体(INT1)和Ge-O顺位的四员环产物(P1);第二条主反应通道所生成的物种为Ge-O对位的扭曲四员环中间体(INT2)和氯迁移产物(P2);P1和INT2分别与甲醛(R2)的进一步作用而导致了两副产物的生成.     

Density Functional Theory Study of Mechanism of Cycloaddition Reaction Between Dimethyl-Silylene Carbene and Acetone

用密度泛函理论研究了单重态二甲基亚硅基卡宾与丙酮环加成反应的反应机理,势能面结果表明该反应有两条相互竞争的主反应通道. 反应规律为：二甲基亚硅基卡宾中的π轨道与π键化合物中π轨道的[2+2]环加成作用造成了扭曲四员环中间体和平面四员环产物的形成;平面四员环产物中卡宾C原子的不饱和性,导致了甲基迁移产物和硅杂双环化合物的生成.     

二甲基亚甲基硅烯与乙烯生成硅杂双环化合物反应机理的从头算研究

用CCSD(T)//MP2/6-31G^*方法研究了单重态二甲基亚烷基硅烯与乙烯生成硅杂双环化合物环加成反应的机理,根据该反应的势能面可以预言,该反应只有一条主反应通道. 该主反应通道所呈现的反应规律为：二甲基亚烷基硅烯中Si原子的3p空轨道与乙烯中的π轨道形成了π→p授受键,生成三元环中间体(INT1);扩环作用使INT1异构化为四元环硅烯(P2);P2中Si原子的sp³杂化使P2进一步与乙烯结合生成了硅杂双环化合物.     

Ab Initio Study of the Mechanism of Forming a Spiro-Si-heterocyclic Ring Compound Involving Ge from Cl_2Ge=Si:and Formaldehyde

The X2Ge=Si:(X = H, Me, F, Cl, Br, Ph, Ar···) is a new species. Its cycloaddition reaction is a new area for the study of silylene chemistry. The mechanism of cycloaddition reaction between singlet Cl2Ge=Si: and formaldehyde has been investigated with CCSD(T)//MP2/6-31G* method. From the potential energy profile, it can be predicted that the reaction has two competitive dominant reaction pathways. The reaction rule presented is that the two reactants firstly form a four-membered Ge-heterocyclic ring silylene through the [2+2] cycloaddition reaction. Owing to the 3p unoccupied orbital of Si: atom in the four-membered Ge-heterocyclic ring silylene and the π orbital of formaldehyde forming a π→p donor-acceptor bond, the four-membered Ge-heterocyclic ring silylene further combines with formaldehyde to form an intermediate. Because the Si: atom in intermediate shows sp3 hybridization after transition state, the intermediate isomerizes to a spiro-Si-heterocyclic ring compound involving Ge via a transition state. Simultaneously, the ring strain of the four-membered Ge-heterocyclic ring silylene makes it isomerize to a twisted four-membered ring product. The research result indicates the laws of cycloaddition reaction between X2Ge=Si:(X = H, Me, F, Cl, Br, Ph, Ar···) and the asymmetric π-bonded compounds, which are significant for the synthesis of small-ring and spiro-Si-heterocyclic ring compound involving Ge. The study extends the research area and enriches the research content of silylene chemistry.