Ab initio study of mechanism of forming a spiro-heterocyclic ring compound involving Si from dichlorosilylenesilylene (Cl2Si=Si:)-> Cl2Si=Si: and aldehyde

作者：Bao Weijie; Shi Leyi; Liu Dongting; Lu Xiuhui^*

来源：Research on Chemical Intermediates, 2013, 39(9): 4127-4136.

DOI：10.1007/s11164-012-0929-7

• Dichlorosilylenesilylene (Cl2Si=Si:) -&gt
• Cl2Si=Si
• Spiro-heterocyclic ring compound
• Cycloaddition reaction

The mechanism of the cycloaddition reaction between singlet dichlorosilylenesilylene (Cl2Si=Si:)-> Cl2Si=Si: and aldehyde has been investigated with the CCSD(T)//MP2/6-31G* method. From the potential energy profile, it could be predicted that the reaction has one dominant reaction pathway. The reaction rules presented is that the two reactants firstly form a four-membered ring silylene through the [2+2] cycloaddition reaction. Because of the 3p unoccupied orbital of Si: atom in the four-membered ring silylene and the pi orbital of aldehyde forming a pi -> p donor-acceptor bond, the four-membered ring silylene further combines with aldehyde to form an intermediate. Because the Si: atom in the intermediate happens sp (3) hybridization after transition state, then the intermediate isomerizes to a spiro-heterocyclic ring compound involving Si via a transition state.

• 出版日期2013-11
• 单位济南大学