Please use this identifier to cite or link to this item:
http://hdl.handle.net/1942/27344
Title: | Theoretical study on the elimination kinetics in the gas phase of allyl methyl compounds | Authors: | Oliaey, Ahmad Reza SHIROUDI, Abolfazl Zahedi, Ehsan DELEUZE, Michael |
Issue Date: | 2018 | Publisher: | SPRINGER WIEN | Source: | MONATSHEFTE FUR CHEMIE, 149(8), p. 1389-1400 | Abstract: | The thermal decomposition kinetics of allyl methyl amine, allyl methyl ether, and allyl methyl sulfide in the gas phase has been studied theoretically using the M06-2x/aug-cc-pVTZ quantum chemical approach. The observed activation parameters are consistent with a concerted unimolecular mechanism involving a non-planar cyclic six-membered transition state. Based on the optimized ground state geometries, a natural bond orbital analysis of donor-acceptor interactions reveals that the stabilization energies corresponding to the electronic delocalization from the lone-pair (LP) non-bonding orbitals on the heteroatom to the neighboring antibonding orbitals decrease from allyl methyl amine to allyl methyl sulfide. This delocalization fairly explains the increase of occupancies of LP orbitals on the heteroatom from allyl methyl sulfide to allyl methyl amine. The results also suggest that the kinetics of the thermolysis of the studied compounds are dominated by electronic delocalization effects. Analysis of bond order, bond indices, and synchronicity parameters demonstrates that these reactions proceed through a concerted and slightly asynchronous mechanism. [GRAPHICS] . | Notes: | [Oliaey, Ahmad Reza] Islamic Azad Univ, Chem Dept, Tonekabon Branch, Tonekabon, Iran. [Shiroudi, Abolfazl] Islamic Azad Univ, East Tehran Branch, Young Researchers & Elite Club, Tehran, Iran. [Zahedi, Ehsan] Islamic Azad Univ, Shahrood Branch, Chem Dept, Shahrood, Iran. [Deleuze, Michael S.] Hasselt Univ, Ctr Mol & Mat Modelling, Agoralaan, B-3590 Diepenbeek, Belgium. | Keywords: | Decomposition; Energy barriers; Chemical kinetics; Reaction mechanisms; NBO; RRKM theory | Document URI: | http://hdl.handle.net/1942/27344 | ISSN: | 0026-9247 | e-ISSN: | 1434-4475 | DOI: | 10.1007/s00706-018-2184-0 | ISI #: | 000439464600009 | Category: | A1 | Type: | Journal Contribution | Validations: | ecoom 2019 |
Appears in Collections: | Research publications |
Files in This Item:
File | Description | Size | Format | |
---|---|---|---|---|
oliaey 1.pdf Restricted Access | Published version | 1.46 MB | Adobe PDF | View/Open Request a copy |
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.