Theoretical study of mechanism of cycloaddition reaction between singlet dichlorosilylene carbene (Cl2Si=C:) and formaldehyde

Abstract

The mechanism of the cycloaddition reaction between singlet dichlorosilylene carbene (Cl2Si=C:) and formaldehyde has been investigated with MP2/6-31G* method, including geometry optimization and vibrational analysis for the involved stationary points on the potential energy surface. The energies of the different conformations are calculated by Zero-point energy and CCSD (T)//MP2/6-31G* method. From the potential energy profile, it can be predicted that the reaction has two competitive dominant reaction pathways. The first dominant reaction pathway consists of two steps: (1) the two reactants (R1, R2) firstly form a four-membered ring intermediate (INT4) through a barrier-free exothermic reaction of 387.9 kJ/mol; (2) intermediate (INT4) then isomerizes to H-transfer product (P4.2) via a transition state (TS4.2) with energy barrier of 4.7 kJ/mol. The second dominant reaction pathway as follows: on the basis of intermediate (INT4) created between R1 and R2, intermediate (INT4) further reacts with formaldehyde (R2) to form the intermediate (INT5) through a barrier-free exothermic reaction of 158.3 kJ/mol. Then, intermediate (INT5) isomerizes to a silicic bis-heterocyclic product (P5) via a transition state (TS5), for which the barrier is 40.1 kJ/mol.