Theoretical Study on the Mechanism of Rearrangement Reactions of Bicyclic Derivatives of Cyclopropane to Monocyclic Derivatives under the Catalysis of Pt-Salt

[Image: see text] In this paper, the mechanistic studies on the isomerization of hydroxyl and silyl derivatives of bicyclic cyclopropanes under the catalytic action of Zeise’s salt have been reported. The catalytic activity of both the monomeric and the dimeric forms of Zeise’s salt has been studied by applying the high-level quantum mechanical method. Results from this investigation reveal that the reaction goes favorably under the catalysis of the dimeric form of Zeise’s salt. The calculated activation barrier for the catalytic process using Zeise’s dimer reveals that the rearrangement occurs with an activation barrier of 19–25 kcal mol(–1). Depending on the nature of substituents present on the substrate, formation of various products has been explained. This study also includes the heteronuclear counter part of Zeise’s dimer where one of the Pt-metals is replaced by palladium (Pd) and nickel (Ni) successively. The calculated activation barrier using these heteronuclear catalysts is found to be close enough to that calculated for the catalytic pathway using Zeise’s dimer.