Chemical bonding in three-membered ring systems

TL;DR

This study investigates the formation and elimination of three-membered ring systems involving silicon and carbon, revealing that these reactions often follow diabatic pathways without energy barriers, and analyzing charge redistribution during these processes.

Contribution

It provides a detailed CAS(4,4) wave function analysis of the diabatic reaction pathways in silicon-carbon three-membered rings, highlighting the role of symmetry changes.

Findings

Reactions often follow diabatic pathways without saddle points.

Symmetry changes lead to adiabatic pathways with single minimum energy paths.

Charge and spin redistribution analyzed using the orthogonal valence bond method.

Abstract

The formation of the four three-ring systems \ce{c-(CH2)_{3-k}(SiH2)_{k}}, ($k=0$: cyclopropane, $k=1$: silirane, $k=2$: disilirane, $k=3$: cyclotrisilane) by addition of methylene and silylene to the double bond in ethene, disilene, and silaethene, as well as the elimination of the carbene analogs from the three-rings, was studied with CAS(4,4) wave functions in both $C_{2v}$ and $C_s$ symmetry. To reveal charge and spin redistribution during these reactions the CAS(4,4) wave functions were analyzed using the orthogonal valence bond method (OVB). The potential energy curves, different internal coordinates, and the results of the OVB analysis show, that frequently the addition and elimination reactions follow different minimum energy paths, because they are indeed diabatic reactions. In these cases, there are no energy barriers corresponding to saddle points on the potential energy surfaces but the energy increases during one diabatic reaction until, at a certain point, the system jumps to the other diabatic state and, in the following, the energy decreases. This happens for reactions in $C_{2v}$ symmetry; as soon as the system can change to the lower symmetry, the diabatic states combine to an adiabatic one and the reaction follows a single minimum energy path.