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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 34, Number 12
BKCSDE 34(12)
December 20, 2013 

 
Title
Ab Initio Study of Mechanism of Forming Spiro-Ge-Heterocyclic Ring Compound From Cl2Ge=Ge: and Formaldehyde
Author
Xiuhui Lu*, Yongqing Li, Jingjing Ming
Keywords
Cl2Ge=Ge: Four-membered Ge-heterocyclic ring germylene, Spiro-Ge-heterocyclic compounds, Potential energy profile
Abstract
The H2Ge=Ge: and its derivatives (X2Ge=Ge:, X = H, Me, F, Cl, Br, Ph, Ar……) is a new species. Its cycloaddition reactions is a new area for the study of germylene chemistry. The mechanism of the cycloaddition reaction between singlet state Cl2Ge=Ge: and formaldehyde has been investigated with CCSD(T)//MP2/6-31G* method. From the potential energy profile, it could be predicted that the reaction has only one dominant reaction pathway. The reaction rule presented is that the two reactants first form a fourmembered Ge-heterocyclic ring germylene through the [2+2] cycloaddition reaction. Because of the 4p unoccupied orbital of Ge: atom in the four-membered Ge-heterocyclic ring germylene and the π orbital of formaldehyde forming a π→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 hybridizes to an sp3 hybrid orbital 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 H2Ge=Ge: and formaldehyde, and laid the theory foundation of the cycloaddition reaction between H2Ge=Ge: and its derivatives (X2Ge=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. The study extends research area and enriches the research content of germylene chemistry.
Page
3690 - 3694
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