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Title: | 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 | Other Titles: | Theoretical study on the mechanisms and kinetics of the beta-elimination of 2,2-dihaloethyltrihalosilanes (X = F, Cl, Br) compounds: a DFT study along with a natural bond orbital analysis | Authors: | Oliaey, Ahmad Reza SHIROUDI, Abolfazl Zahedi, Ehsan DELEUZE, Michael |
Issue Date: | 2018 | Source: | Reaction Kinetics Mechanisms and Catalysis, 124 (1), p. 27-44 | 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 σC1−C2 bonding orbitals to σ∗C2−Si3 antibonding orbitals, increase from 2,2-difluoroethyltrifluorosilane to 2,2-dichloroethyltrichlorosilane and then to 2,2-dibromoethyltriboromosilane. The decrease of σC1−C2 bonding orbitals occupancies and increase of the σ∗C2−Si3 antibonding orbitals occupancies through σC1−C2→σ∗C2−Si3 delocalizations could facilitate the β-elimination of the 2,2-difluoroethyltrifluorosilane compound, compared to 2,2-dichloroethyltrichlorosilane and 2,2-dibromoethyltriboromosilane. | Notes: | Shiroudi, A (reprint author), Islamic Azad Univ, East Tehran Branch, Young Researchers & Elite Club, Tehran, Iran. abolfazl.shiroudi@uhasselt.be | Keywords: | energy barriers; β-elimination processes; rate constants; NBO; reaction mechanisms | Document URI: | http://hdl.handle.net/1942/26135 | ISSN: | 1878-5190 | e-ISSN: | 1878-5204 | DOI: | 10.1007/s11144-017-1332-6 | ISI #: | 000430556600003 | Rights: | (C) Akadémiai Kiado, Budapest, Hungary 2017 | Category: | A1 | Type: | Journal Contribution | Validations: | ecoom 2019 |
Appears in Collections: | Research publications |
Files in This Item:
File | Description | Size | Format | |
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11144_2017_1332_MOESM1_ESM.pdf | Supplementary material | 105.91 kB | Adobe PDF | View/Open |
10.1007_s11144-017-1332-6.pdf Restricted Access | Published version | 493.72 kB | Adobe PDF | View/Open Request a copy |
Manuscript_v2_F (1).pdf | Peer-reviewed author version | 548.69 kB | Adobe PDF | View/Open |
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