{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,6]],"date-time":"2026-03-06T14:23:13Z","timestamp":1772806993193,"version":"3.50.1"},"reference-count":53,"publisher":"MDPI AG","issue":"11","license":[{"start":{"date-parts":[[2016,11,11]],"date-time":"2016-11-11T00:00:00Z","timestamp":1478822400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>The kinetics of the reaction between triphenylphosphine (TPP) and dimethyl acetylenedicarboxylate (DMAD) in the presence of Meldrum\u2019s acid (MA) for the generation of the 1,4-diionic organophosphorus compound has been investigated using the stopped-flow and UV-VIS spectrophotometry techniques. The first step of the reaction between TPP and DMAD for the generation of (I1) in ethanol was followed by the stopped-flow apparatus. This step was recognized as a fast step. The reaction between the intermediate (I1) and MA showed first-order kinetics, and it was followed by the UV-VIS spectrophotometry technique. The activation parameters for the slow step of the proposed mechanism were determined using two linearized forms of the Eyring equation. From the temperature, concentration and solvent studies, the activation energy (Ea = 20.16 kJ\u00b7mol\u22121) and the related activation parameters (\u0394G\u2021 = 71.17 \u00b1 0.015 kJ\u00b7mol\u22121, \u0394S\u2021 = \u2212185.49 \u00b1 0.026 J\u00b7mol\u22121 and \u0394H\u2021 =17.72 \u00b1 0.007 kJ\u00b7mol\u22121) were calculated. The experimental data indicated that the reaction was zero-order in MA and second-order overall. The proposed mechanism was confirmed with the observed kinetic data obtained from the UV-VIS and stopped-flow techniques.<\/jats:p>","DOI":"10.3390\/molecules21111514","type":"journal-article","created":{"date-parts":[[2016,11,11]],"date-time":"2016-11-11T10:05:56Z","timestamp":1478858756000},"page":"1514","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":13,"title":["Kinetic Spectrophotometric Method for the 1,4-Diionic Organophosphorus Formation in the Presence of Meldrum\u2032s Acid: Stopped-Flow Approach"],"prefix":"10.3390","volume":"21","author":[{"given":"Fatemeh","family":"Ghodsi","sequence":"first","affiliation":[{"name":"Department of Chemistry, University of Sistan and Baluchestan, P.O. Box 98135-674, Zahedan 9816744599, Iran"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Sayyed","family":"Habibi-Khorassani","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Sistan and Baluchestan, P.O. Box 98135-674, Zahedan 9816744599, Iran"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Mehdi","family":"Shahraki","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Sistan and Baluchestan, P.O. Box 98135-674, Zahedan 9816744599, Iran"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2016,11,11]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"415","DOI":"10.1039\/a906631d","article-title":"Effects of methylene chains on photoreactions of diphenylalkanediones and phenylalkenons","volume":"3","author":"Nakamura","year":"2000","journal-title":"J. Chem. Soc. 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