Ab initio study of mechanism of cycloaddition reaction between H2Ge = Ge: and acetone

作者：Ming Jingjing; Li Yongqing; Lu Xiuhui^*

来源：Structural Chemistry, 2014, 25(6): 1669-1675.

DOI：10.1007/s11224-014-0437-z

• H2Ge = Ge
• Spiro-Ge-heterocyclic compound
• Potential energy profile

The mechanism of the cycloaddition reaction between singlet H2Ge = Ge: and acetone has been investigated with CCSD(T)//MP2/6-31G* method. From the potential energy profile, it could be predicted that the reaction has two competitive dominant reaction pathways. The reaction rule presented is that the two reactants firstly form a four-membered 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 acetone forming a pi -> p donor-acceptor bond, the four-membered Ge-heterocyclic ring germylene further combines with acetone to form an intermediate. Because the Ge atom in intermediate happens sp(3) hybridization after transition state, then, intermediate isomerizes to a spiro-Ge-heterocyclic ring compound via a transition state. Simultaneously, the ring strain of the four-membered Ge-heterocyclic ring germylene makes it isomerize to a twisted four-membered ring product.

• 出版日期2014-12
• 单位济南大学