Ab initio study of mechanism of forming a spiro-ge-heterocyclic ring compound

作者：Lu Xiuhui^*; Ji Hua

来源：Structural Chemistry, 2013, 24(1): 159-164.

DOI：10.1007/s11224-012-0046-7

• Dichloromethylenegermene
• Spiro-heterocyclic ring compound
• Potential energy profile

The mechanism of cycloaddition reaction between singlet state dichloromethylenegermene (Cl2C=Ge:) and ethene has been investigated with the CCSD(T)//B3LYP/6-31G* method. From the potential energy profile, it could be predicted that the reaction has one dominant reaction channel. The reaction rule presented is that the 4p unoccupied orbital of Ge in dichloromethylenegermene and the pi orbital of ethene forming a pi -> p donor-acceptor bond resulting in the formation of a three-membered ring intermediate. Ring-enlargement effect make the three-membered ring intermediate isomerizes to a four-membered ring germylidene. Because the 4p unoccupied orbital of Ge atom in the four-membered ring germylidene and the pi orbital of ethene form a pi -> p donor-acceptor bond, the four-membered ring germylidene further combines with ethene to form another intermediate. Because the Ge atom in the intermediate happens sp (3) hybridization after transition state, the intermediate isomerizes to a spiro-Ge-heterocyclic ring compound.

• 出版日期2013-2
• 单位山东医学高等专科学校; 济南大学