Abstract
The β-elimination kinetics of 2,2-dihaloethyltrihalosilanes in the gas phase has been studied computationally using density functional theory (DFT) along with the M06-2x exchange–correlation functional and the aug-cc-pVTZ basis set. The calculated energy profiles have been supplemented with calculations of rate constants under atmospheric pressure and in the fall-off regime, by means of transition state theory (TST), variational transition state theory (VTST), and statistical Rice–Ramsperger–Kassel–Marcus (RRKM) theory. Activation energies and rate constants obtained using the M06-2x/aug-cc-pVTZ approaches are in good agreement with the available experimental data. Analysis of bond order, natural bond orbitals, and synchronicity parameters suggests that the β-elimination of the studied compounds can be described as concerted and slightly asynchronous. The transition states of these reactions correspond to four-membered cyclic structures. Based on the optimized ground state geometries, a natural bond orbital (NBO) analysis of donor–acceptor interactions also show that the resonance energies related to the electronic delocalization from \(\sigma_{{{\text{C}}_{ 1} {-}{\text{C}}_{ 2} }}\) bonding orbitals to \(\sigma^{*}_{{{\text{C}}_{ 2} - {\text{Si}}_{ 3} }}\) antibonding orbitals, increase from 2,2-difluoroethyltrifluorosilane to 2,2-dichloroethyltrichlorosilane and then to 2,2-dibromoethyltriboromosilane. The decrease of \(\sigma_{{{\text{C}}_{ 1} {-}{\text{C}}_{ 2} }}\) bonding orbitals occupancies and increase of the \(\sigma^{*}_{{{\text{C}}_{ 2} - {\text{Si}}_{ 3} }}\) antibonding orbitals occupancies through \(\sigma_{{{\text{C}}_{ 1} - {\text{C}}_{ 2} }} \to \sigma^{*}_{{{\text{C}}_{ 2} - {\text{Si}}_{ 3} }}\) delocalizations could facilitate the β-elimination of the 2,2-difluoroethyltrifluorosilane compound, compared to 2,2-dichloroethyltrichlorosilane and 2,2-dibromoethyltriboromosilane.
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Supplementary material 1 (PDF 105 kb). Table S1 Unimolecular rate constants for all reaction steps involved in the reported chemical pathways (results obtained by means of RRKM theory at different pressures and temperatures, according to the computed M06-2x/aug-cc-pVTZ energy profiles)
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Oliaey, A.R., Shiroudi, A., Zahedi, E. et al. Theoretical study on the mechanisms and kinetics of the β-elimination of 2,2-dihaloethyltrihalosilanes (X = F, Cl, Br) compounds: a DFT study along with a natural bond orbital analysis. Reac Kinet Mech Cat 124, 27–44 (2018). https://doi.org/10.1007/s11144-017-1332-6
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DOI: https://doi.org/10.1007/s11144-017-1332-6