DFT INSIGHTS INTO THE EFFECT OF SUBSTITUENTS ON THE REARRANGEMENT OF SILYLOXYACETYLENES TO SILYLKETENES
The current study investigates the rearrangement reaction mechanism of silylketenes from Silyloxyethyne, 1- Silyloxypropyne and 2-Silylsilyloxyethyne via three paths (Path 1, 2, and 3) using DFT calculations. All the threerearrangement reactions are exothermic, with Path 2 being the least exothermic. A planar four-membered transitionstructure with a single imaginary frequency (~ 400) is obtained for all the three paths. Only minor variations inΔEvalues are observed among the three pathways. Also, the introduction of methyl and silyl groups has no significant effect on the activation energy of the three reaction paths. The formation of C-Si and dissociation of the O-Si bondare indicated by structural parameters, charge density, Laplacian density, and natural atomic charge values. Our results indicate that DFT calculations provide reliable results at a low computational cost. Theoretical study of thesereactions is important, as the product silylketene undergoes side reactions with the reactant itself, makingexperimental determination of reaction enthalpy challenging. This work provides insight into the reactionmechanisms, the effect of substituents (methyl and silyl groups), and contributes to the advancement of qualityeducation.
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