Ab initio study of the mechanism of formation of a spiro Si-heterocyclic ring compound involving Ge from H2Ge=Si: and acetaldehyde

作者：Lu, Xiuhui^*; Ming, Jingjing

来源：Journal of the Serbian Chemical Society, 2016, 81(6): 633-643.

DOI：10.2298/JSC151130014L

• H2Ge=Si
• four-membered Ge-heterocyclic ring silylene
• spiro Si-heterocyclic ring compound
• potential energy profile

H2Ge=Si: and its derivatives (X2Ge=Si:, X =H, Me, F, Cl, Br, Ph, Ar,.) are new species. The cycloaddition reactions of H2Ge=Si: is a new area for the study of silylene chemistry. The mechanism of the cycloaddition reaction between singlet H2Ge=Si: and acetaldehyde was investigated using the MP2/6-311++G** method. From the potential energy profile, it could be predicted that the reaction has a dominant reaction pathway. The reaction rule presented is that the two reactants firstly form a four-membered Ge-heterocyclic ring silylene through a [2+2] cycloaddition reaction. As the 3p unoccupied orbital of the Si: atom in the four-membered Ge-heterocyclic ring silylene and the pi orbital of acetaldehyde form a pi -> p donor-acceptor bond, the four-membered Ge-heterocyclic ring silylene further combines with acetaldehyde to form an intermediate. Then the intermediate isomerizes via a transition state to a spiro-Si-heterocyclic ring compound involving Ge.

• 出版日期2016
• 单位济南大学