DFT Calculations of the Elimination Kinetics of Silacyclobutanes and its Methyl Derivatives in the Gas-Phase

Abstract

The gas-phase thermal decomposition kinetics of silacyclobutane (1), 1-methyl- silacyclobutane (2), and 1,1-dimethyl-1-silacyclobutane (3) has been theoretically studied at the B3LYP/6-311G**, B3PW91/6-311G**, and MPW1PW91/6-311G** levels. The B3LYP/6-311G** method was found to give a reasonable good agreement with the experimental kinetics and thermodynamic parameters. The decomposition reaction of compounds 1–3 yields ethylene and the corresponding silene. Based on the optimized ground state geometries using B3LYP/6-311G** method, the natural bond orbital (NBO) analysis of donor-acceptor (bonding–antibonding) interactions revealed that the perturbation energies (E₂) associated with the electronic delocalization from σ_Si1–C2 to σ*_C4–Si1 orbitals increase from compounds 1 to 3. The σ_Si1–C2→σ*_C4–Si1 resonance energies for compounds 1–3 are 1.17, 1.26, and 1.43 kcal/mol, respectively. Also, the decomposition process in these compounds is controlled by σ→σ* resonance energies. Moreover, the obtained order of energy barriers could be explained by the number of electron-releasing methyl groups substituted to the Si_sp2 atom. NBO analysis shows that the occupancies of σ_Si1–C2 bonds decrease for compounds 1–3 as 3 < 2 < 1, and the occupancies of σ*_Si1–C2 bonds increase in the opposite order (3 > 2 > 1). Moreover, these results can fairly explain the decrease of the energy barriers (ΔE_o) of the decomposition reaction of compounds 1 to 3. The calculated data demonstrate that in the decomposition process of the studied compounds, the polarization of the C₃–C₄ bond is the rate determining factor. Analysis of bond orders, NBO charges, bond indexes, synchronicity parameters, and IRC calculations indicate that these reactions are occurring through a concerted and asynchronous four-membered cyclic transition state type of mechanism.

GRAPHICAL ABSTRACT

Keywords:

• Thermal decomposition
• DFT
• NBO
• IRC
• silacyclobutanes