The mechanism of the cycloaddition reaction of forming a silicic bis-heterocyclic compound between singlet dimethylmethylenesilylene (Me2C=Si:) and ethene has been investigated with the CCSD(T)//MP2/6-31G* method. From the potential energy profile, it can be predicted that, this reaction has one dominant channel. The presented rule of this dominant channel: the 3p unoccupied orbital of Si in dimethylmethylenesilylene and the π orbital of ethene forming the π→p donor-acceptor bond, resulting in the formation of three-membered ring intermediate (INT1); INT1 then isomerizes to a four-membered ring silylene (P2), which is driven by ring-enlargement effect; due to sp3 hybridization of Si atom in P2, P2 further combines with ethene to form a silicic bis-heterocyclic compound.
The mechanism of the cycloaddition reaction between singlet dimethyl-silylene carbene and acetone has been investigated with density functional theory, From the potential energy profile, it can be predicted that the reaction has two competitive dominant reaction pathways. The presented rule of this reaction: the [2+2] cycloaddition effect between the π orbital of dimethyl-silylene carbene and the π orbital of π-bonded compounds leads to the formation of a twisty four-membered ring intermediate and a planar four-membered ring product; The unsaturated property of C atom from carbene in the planar four-membered ring product, resulting in the generation of CH3-transfer product and silicic bis-heterocyclic compound.
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