Citation: LU Xiu-Hui, WANG Dang-Sheng, LI Tao, LIAN Zhen-Xia. Ab Initio Study of the Mechanism of Forming a Spiro-Ge-heterocyclic Ring Compound Involving Si from Me₂Si=Ge: and Formaldehyde[J]. Chinese Journal of Structural Chemistry, ;2015, 34(4): 481-487. doi: 10.14102/j.cnki.0254-5861.2011-0551 shu

Ab Initio Study of the Mechanism of Forming a Spiro-Ge-heterocyclic Ring Compound Involving Si from Me₂Si=Ge: and Formaldehyde

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

Received Date: 30 October 2014
Available Online: 7 January 2015

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.
- Me₂Si=Ge:,
- four-membered Si-heterocyclic ring germylene,
- spiro-Ge-heterocyclic ring compounds,
- potential energy profile
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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Ab Initio Study of the Mechanism of Forming a Spiro-Ge-heterocyclic Ring Compound Involving Si from Me2Si=Ge: and Formaldehyde

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通讯作者: 陈斌, bchen63@163.com

Ab Initio Study of the Mechanism of Forming a Spiro-Ge-heterocyclic Ring Compound Involving Si from Me₂Si=Ge: and Formaldehyde