Ab initio study of mechanism of forming a spiro-Si-heterocyclic compound involving Ge from (CH3)(2)Ge=Si: and formaldehyde

作者：Ming Jingjing; Han Junfeng; Lu Xiuhui^*

来源：Heterocyclic Communications, 2014, 20(4): 243-249.

DOI：10.1515/hc-2014-0066

• (CH3)(2)Ge=Si
• four-membered Ge-heterocyclic silylene
• potential energy profile
• spiro-Si-heterocyclic compounds

(CH3)(2)Ge=Si: and its derivatives (X2Ge=Si:, X = H, F, Cl, Br, Ph, Ar) are a new species. Their cycloaddition reaction is a new area for the study of silylene chemistry. The mechanism of the cycloaddition reaction between singlet (CH3)(2)Ge=Si: and formaldehyde was investigated with the CCSD(T)//MP2/6-31G* method. From the potential energy profile, it can be predicted that the reaction has one dominant pathway. The reaction rule presented is that the two reactants first form a four-membered Ge-heterocyclic silylene through the [2+2] cycloaddition reaction. Because of the 3p unoccupied orbital of Si: atom in the four-membered Geheterocyclic silylene and the pi orbital of formaldehyde forming a pi -> p donor-acceptor bond, the four-membered Ge-heterocyclic silylene further combines with formaldehyde to form an intermediate product. The Si: atom in the intermediate product is sp(3) hybridized after transition state, and this intermediate isomerizes to a spiro-Si-heterocyclic compound involving Ge via a transition state.

• 出版日期2014-8
• 单位济南大学