论文部分内容阅读
X2Si=Ge:(X = H, Me, F, Cl, Br, Ph, Ar···) is a new species. Its cycloaddition reaction is a new area for the study of germylene chemistry. The mechanism of cycloaddition reaction between singlet state Me2Si=Ge: and formaldehyde has been investigated with the CCSD(T)//MP2/cc-pvtz method. From the potential energy profile, it could be predicted that the reaction has one dominant reaction pathway. The reaction rule presented is that the two reactants first form a four-membered Si-heterocyclic ring germylene through the [2+2] cycloaddition reaction. Because of the 4p unoccupied orbital of Ge: atom in the four-membered Si-heterocyclic ring germylene and the π orbital of formaldehyde form a π→p donor-acceptor bond, the four-membered Si-heterocyclic ring germylene further combines with formaldehyde to form an intermediate. Because the Ge atom in the intermediate undergoes sp3 hybridization after transition state, then the intermediate isomerizes to a spiro-Ge-heterocyclic ring compound involving Si via a transition state. The research result indicates the laws of cycloaddition reaction between H2Si=Ge: and formaldehyde. It has important reference value for the cycloaddition reaction between X2Si=Ge:(X= H, Me, F, Cl, Br, Ph, Ar···) and asymmetric π-bonded compounds, which is significant for the synthesis of small-ring and spiro-Ge-heterocyclic compounds involving Si. The study extends research area and enriches the research content of germylene chemistry.
X2Si = Ge: (X = H, Me, F, Cl, Br, Ph, Ar ...) is a new species. Its cycloaddition reaction is a new area for the study of germylene chemistry. The mechanism of cycloaddition reaction between singlet state Me2Si = Ge: and formaldehyde has been investigated with the CCSD (T) // MP2 / cc-pvtz method. From the potential energy profile, it could be predicted that the reaction has one dominant reaction pathway. The reaction rule presented is that The two reactants first form a four-membered Si-heterocyclic ring germylene through the [2 + 2] cycloaddition reaction. Because of the 4p unoccupied orbital of Ge: atom in the four-membered Si-heterocyclic ring germylene and the π orbital of formaldehyde form a π → p donor-acceptor bond, the four-membered Si-heterocyclic ring germylene further combines with formaldehyde to form an intermediate. Since the Ge atom in the intermediate undergoes sp3 hybridization after transition state, then the intermediate isomerizes to a spiro- Ge-heterocyclic ring compound involving Si via a transition state. The research result indicates the laws of cycloaddition reaction between H2Si = Ge: and formaldehyde. It has important reference value for the cycloaddition reaction between X2Si = Ge: (X = H, Me, F, Cl, Br , Ph, Ar ···) and asymmetric π-bonded compounds, which are significant for the synthesis of small-ring and spiro-Ge-heterocyclic compounds involving Si. The study extends research area and enriches the research content of germylene chemistry.