caa a22 4500 44538879X CHVBK 20180317143040.0 cr unu---uuuuu 170323e20110201xx s 000 0 eng 10.1007/s11144-010-0254-3 doi (NATIONALLICENCE)springer-10.1007/s11144-010-0254-3 Control aromaticity in the thermal decomposition of 2,5-dihydrofuran, 2,5-dihydrothiophene and 3-pyrroline: a kinetic and thermodynamic study via DFT [Elektronische Daten] [Abolfazl Shiroudi, Ehsan Zahedi, Reza Zabihi] A theoretical study of the thermal decomposition kinetics of 2,5-dihydrofuran (1), 2,5-dihydrothiophene (2), and 3-pyrroline (3) has been carried out at the B3LYP/6-31++G**, B3PW91/6-31++G** and MPW1PW91/6-31++G** levels of theory. Our results show that the MPW1PW91/6-31++G** method is in good agreement with the available experimental values. The nucleus independent chemical shift (NICS) values of all reactants, TSs and products indicate that all studied structures are aromatic and the studied reactions are controlled kinetically and thermodynamically by the change of the aromaticity. Based on the optimized ground state geometries using the MPW1PW91/6-31++G** method, the natural bond orbital analysis (NBO) of donor-acceptor (bonding-antibonding) interactions revealed that by the increase of electronegativity of atom $$ {\text{X }}\left( {{\text{O}},{\text{ S}},{\text{ NH}}} \right),{\text{ LP}}\left( {\text{e}} \right)_{\text{X1}} \to \sigma_{{{\text{C}}_{ 2} - {\text{H}}_{ 6} }}^{*} $$ resonance energies and also, the HOMO-LUMO energy-gaps in the ground state structures increase. The results also suggest that in compounds 1-3, the hydrogen elimination are controlled by LP(e)→σ* resonance energies. Akadémiai Kiadó, Budapest, Hungary, 2010 DFT nationallicence Decomposition nationallicence NBO nationallicence NICS nationallicence GIAO nationallicence Shiroudi Abolfazl Chemistry Department, Islamic Azad University, Shahrood Branch, P.O.box 36155/133, Shahrood, Iran aut Zahedi Ehsan Chemistry Department, Islamic Azad University, Shahrood Branch, P.O.box 36155/133, Shahrood, Iran aut Zabihi Reza Chemistry Department, Islamic Azad University, Karaj Branch, Tehran, Iran aut Reaction Kinetics, Mechanisms and Catalysis Springer Netherlands 102/1(2011-02-01), 21-35 1878-5190 102:1<21 2011 102 11144 https://doi.org/10.1007/s11144-010-0254-3 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/s11144-010-0254-3 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Shiroudi Abolfazl Chemistry Department, Islamic Azad University, Shahrood Branch, P.O.box 36155/133, Shahrood, Iran aut NATIONALLICENCE 700 1- Zahedi Ehsan Chemistry Department, Islamic Azad University, Shahrood Branch, P.O.box 36155/133, Shahrood, Iran aut NATIONALLICENCE 700 1- Zabihi Reza Chemistry Department, Islamic Azad University, Karaj Branch, Tehran, Iran aut NATIONALLICENCE 773 0- Reaction Kinetics, Mechanisms and Catalysis Springer Netherlands 102/1(2011-02-01), 21-35 1878-5190 102:1<21 2011 102 11144 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer