Citation: LU Xiu-Hui, LI Yong-Qing, MING Jing-Jing. Ab Initio Study of the Mechanism of Cycloaddition Reaction between H₂Ge=Ge: and Acetaldehyde[J]. Chinese Journal of Structural Chemistry, ;2015, 34(1): 7-14. doi: 10.14102/j.cnki.0254-5861.2011-0476 shu

Ab Initio Study of the Mechanism of Cycloaddition Reaction between H₂Ge=Ge: and Acetaldehyde

1.
School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, China

Received Date: 12 August 2014
Available Online: 13 October 2014
Fund Project: The work was supported by the National Natural Science Foundation of China (No. 51102114) (No. 51102114)

The mechanism of cycloaddition reaction between singlet state H₂Ge=Ge: and acetaldehyde has been investigated with the MP2/6-311++G** method. From the potential energy profile, it could 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 germylene through the [2+2] cycloaddition reaction. As the 4p unoccupied orbital of Ge: atom in the four-membered Ge-heterocyclic ring germylene and the π orbital of acetaldehyde form a π→p donor-acceptor bond, the four-membered Ge-heterocyclic ring germylene further combines with acetaldehyde to give an intermediate. Because the Ge atom in intermediate exhibits sp³ hybridization after transition state, the intermediate isomerizes to a spiro-Ge-heterocyclic ring compound via a transition state. Simultaneously, the ring strain of the four-membered Ge-heterocyclic ring germylene makes it isomerize to a twisted four-membered ring product.
- H₂Ge=Ge:,
- four-membered Ge-heterocyclic ring germylene,
- spiro-Ge-heterocyclic compound,
- potential energy profile
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