Ab initio study of mechanism of forming a spiro-Ge-heterocyclic ring compound from H2Ge=Ge: and formaldehyde

作者：Lu Xiuhui^*; Li Yongqing; Bao Weijie; Liu Dongting

来源：Computational and Theoretical Chemistry, 2013, 1007: 76-81.

DOI：10.1016/j.comptc.2012.11.027

• H2Ge=Ge
• Spiro-Ge-heterocyclic ring compound
• Cycloaddition reaction

The mechanism of the cycloaddition reaction between singlet H2Ge=Ge: and formaldehyde has been investigated with the CCSD(T)//MP2/6-31G* 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 [2 + 2] cycloaddition reaction between two reactants firstly generates a four-membered Ge-heterocyclic ring germylene. Because the 4p unoccupied orbital of Ge: atom in the four-membered Ge-heterocyclic ring germylene and the pi orbital of formaldehyde form a pi -> p donor-acceptor bond, the four-membered Ge-heterocyclic ring germylene further combines with formaldehyde to form an intermediate. Because the Ge: atom in intermediate happens sp(3) hybridization after transition state, then, intermediate isomerizes to a spiro-Ge-heterocyclic ring compound via a transition state. The research result indicates the laws of cycloaddition reaction between (HGe)-Ge-2=Ge: and its derivatives(X2Ge=Ge:, X = F, Cl, CH3, Ph, Ar...) and the asymmetric pi-bonded compounds, which is significant for the synthesis of small-ring and spiro-Ge-heterocyclic compounds. The study extends research area and enriches the research content of germylene chemistry.

• 出版日期2013-3-1
• 单位济南大学