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Ab Initio Study of Mechanism of Forming Spiro-Ge-Heterocyclic Ring Compound From C2Ge=Ge: and Formaldehyde
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  • Ab Initio Study of Mechanism of Forming Spiro-Ge-Heterocyclic Ring Compound From C2Ge=Ge: and Formaldehyde
  • Ab Initio Study of Mechanism of Forming Spiro-Ge-Heterocyclic Ring Compound From C2Ge=Ge: and Formaldehyde
저자명
Lu. Xiuhui,Li. Yongqing,Ming. Jingjing
간행물명
Bulletin of the Korean Chemical Society
권/호정보
2013년|34권 12호|pp.3690-3694 (5 pages)
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대한화학회
파일정보
정기간행물|ENG|
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이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
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기타언어초록

The $H_2Ge=Ge:$ and its derivatives ($X_2Ge=Ge:$, X = H, Me, F, Cl, Br, Ph, Ar${ldots}{ldots}$) 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 ${pi}$ orbital of formaldehyde forming a ${pi}{ ightarrow}p$ 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 $sp^3$ 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 $H_2Ge=Ge:$ and formaldehyde, and laid the theory foundation of the cycloaddition reaction between $H_2Ge=Ge:$ and its derivatives ($X_2Ge=Ge:$, X = H, Me, F, Cl, Br, Ph, Ar${ldots}{ldots}$) and 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.