Citation: MING Jing-Jing, HAN Jun-Feng, LU Xiu-Hui. Ab Initio Study of the Mechanism of Forming a Spiro-Si-heterocyclic Ring Compound Involving Ge from Cl₂Ge=Si:and Formaldehyde[J]. Chinese Journal of Structural Chemistry, ;2014, 33(9): 1267-1274. shu

Ab Initio Study of the Mechanism of Forming a Spiro-Si-heterocyclic Ring Compound Involving Ge from Cl₂Ge=Si:and Formaldehyde

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

Received Date: 12 December 2013
Available Online: 1 July 2014
Fund Project: The work was supported by the National Natural Science Foundation of China (No. 51102114) (No. 51102114)

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.
- Cl₂Ge=Si:,
- four-membered Ge-heterocyclic ring silylene,
- spiro-Si-heterocyclic ring compound,
- potential energy profile
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