naa a22 4500 510735118 CHVBK 20180411083007.0 cr unu---uuuuu 180411e20130301xx s 000 0 eng 10.1007/s12039-013-0383-0 doi (NATIONALLICENCE)springer-10.1007/s12039-013-0383-0 AIM analysis, synthetic, kinetic and mechanistic investigations of the reaction between triphenylphosphine and dialkyl acetylenedicarboxylate in the presence of 3-methoxythiophenol [Elektronische Daten] [SAYYED KHORASSANI, MALEK MAGHSOODLOU, HOJJAT GHASEMPOUR, MOHAMMAD ZAKARIANEZHAD, MAHMOUD NASSIRI, ZAHRA GHAHGHAIE] Triphenylphosphine reacts with dialkyl acetylenedicarboxylates in the presence of 3-methoxythiophenol to generate stable phosphorus ylides. These stable ylides exist in solution as a mixture of two geometrical isomers as a result of restricted rotation around the carbon-carbon partial double bond resulting from conjugation of the ylide moiety with the adjacent carbonyl group. Quantum mechanical calculations were employed to check the stability of the two geometrical isomers in phosphorous ylide by natural population analysis (NPA), atoms in molecules (AIM) methods and CHelpG keyword. To determine the kinetic parameters and mechanistic investigation of the reaction, they were monitored by UV spectrophotometry. The second order fits were automatically drawn, and the value of the second order rate constants (k 2) were automatically calculated using standard equations. At the temperature range studied, the dependence of the second order rate constant (ln k 2) on reciprocal temperature was in good agreement with the Arrhenius equation. This provided the relevant plots to calculate the activation energy of all the reactions. Furthermore, useful information was obtained from studies of the effect of solvent, structure of reactions (different alkyl groups within the dialkyl acetylenedicarboxylates), and also concentration of reactants on the rate of reaction. The proposed mechanism was confirmed according to the obtained experimental results, and a steady state approximation. The first (k 2) and third (k 3) steps of the reactions were recognized as the rate determining and fast steps, respectively on the basis of experimental data. Also, the activation parameters involving ΔG# , ΔS# and ΔH# were obtained for all the reactions. Graphical Abstract Triphenylphosphine reacts with dialkyl acetylenedicarboxylates in the presence of 3-methoxythiophenol to generate stable phosphorus ylides. Quantum mechanical calculations were employed to check the stability of the two geometrical isomers of phosphorous ylides. Indian Academy of Sciences, 2013 Kinetic study nationallicence UV spectrophotometry nationallicence geometrical isomers nationallicence stable phosphorus ylides nationallicence KHORASSANI SAYYED Department of Chemistry, The University of Sistan and Baluchestan, 98135-674, Zahedan, Iran aut MAGHSOODLOU MALEK Department of Chemistry, The University of Sistan and Baluchestan, 98135-674, Zahedan, Iran aut GHASEMPOUR HOJJAT Department of Chemistry, Kerman Branch, Islamic Azad University, 76351-31167, Kerman, Iran aut ZAKARIANEZHAD MOHAMMAD Department of Chemistry, Payam Noor University, 19395-3697, Tehran, Iran aut NASSIRI MAHMOUD Department of Maritime, The University of Chabahar, 99717-56499, Chabahar, Iran aut GHAHGHAIE ZAHRA Department of Chemistry, The University of Sistan and Baluchestan, 98135-674, Zahedan, Iran aut Journal of Chemical Sciences Springer-Verlag 125/2(2013-03-01), 387-399 0974-3626 125:2<387 2013 125 12039 https://doi.org/10.1007/s12039-013-0383-0 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/s12039-013-0383-0 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- KHORASSANI SAYYED Department of Chemistry, The University of Sistan and Baluchestan, 98135-674, Zahedan, Iran aut NATIONALLICENCE 700 1- MAGHSOODLOU MALEK Department of Chemistry, The University of Sistan and Baluchestan, 98135-674, Zahedan, Iran aut NATIONALLICENCE 700 1- GHASEMPOUR HOJJAT Department of Chemistry, Kerman Branch, Islamic Azad University, 76351-31167, Kerman, Iran aut NATIONALLICENCE 700 1- ZAKARIANEZHAD MOHAMMAD Department of Chemistry, Payam Noor University, 19395-3697, Tehran, Iran aut NATIONALLICENCE 700 1- NASSIRI MAHMOUD Department of Maritime, The University of Chabahar, 99717-56499, Chabahar, Iran aut NATIONALLICENCE 700 1- GHAHGHAIE ZAHRA Department of Chemistry, The University of Sistan and Baluchestan, 98135-674, Zahedan, Iran aut NATIONALLICENCE 773 0- Journal of Chemical Sciences Springer-Verlag 125/2(2013-03-01), 387-399 0974-3626 125:2<387 2013 125 12039 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer