Ab Initio Study of Mechanism of Forming Spiro-Heterocyclic Ring Compound Involving Si and Ge from Dichlorosilylene Germylidene (Cl₂Si=Ge:) and Acetone

摘要

The mechanism of the cycloaddition reaction between singlet state dichlorosilylene germylidene (Cl2Si=Ge:) and acetone has been investigated with B3LYP/6-31G* and B3LYP/6-31G** method, from the potential energy profile, we predict that the reaction has one dominant reaction pathway. The presented rule of the reaction is that the two reactants firstly form a Si-heterocyclic four-membered ring germylene through the [2+2] cycloaddition reaction. Because of the 4p unoccupied orbital of Ge atom in the Si-heterocyclic fourmembered ring germylene and the π orbital of acetone forming a π→p donor-acceptor bond, the Siheterocyclic four-membered ring germylene further combines with acetone to form an intermediate. Because the Ge atom in the intermediate hybridizes to an sp3 hybrid orbital after the transition state, then, the intermediate isomerizes to spiro-heterocyclic ring compound involving Si and Ge (P4) via a transition state.