title: Kinetic Spectrophotometric Method for the 1,4-Diionic Organophosphorus Formation in the Presence of Meldrum's Acid: Stopped-Flow Approach.
abstract: The kinetics of the reaction between triphenylphosphine (TPP) and dimethyl acetylenedicarboxylate (DMAD) in the presence of Meldrum's 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·mol-1) and the related activation parameters (ΔG‡= 71.17 ± 0.015 kJ·mol-1, ΔS‡= -185.49 ± 0.026 J·mol-1and ΔH‡=17.72 ± 0.007 kJ·mol-1) 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.
authors.affiliation: Department of Chemistry, University of Sistan and Baluchestan, P.O. Box 98135-674, Zahedan 9816744599, Iran. fa.ghodsi@yahoo.com.
authors.forename: Fatemeh
authors.initials: F
authors.lastname: Ghodsi
authors.affiliation: Department of Chemistry, University of Sistan and Baluchestan, P.O. Box 98135-674, Zahedan 9816744599, Iran. smhabibikhorassani@yahoo.com.
authors.forename: Sayyed Mostafa
authors.initials: SM
authors.lastname: Habibi-Khorassani
authors.affiliation: Department of Chemistry, University of Sistan and Baluchestan, P.O. Box 98135-674, Zahedan 9816744599, Iran. mehdishahraki@chem.usb.ac.ir.
authors.forename: Mehdi
authors.initials: M
authors.lastname: Shahraki
mesh_terms: D060326:Chemistry Techniques, Synthetic; D004146:Dioxanes / Q000737:chemistry*; D007700:Kinetics; D009930:Organic Chemicals / Q000138:chemical synthesis / Q000737:chemistry*; D010758:Phosphorus / Q000737:chemistry*; D013053:Spectrophotometry / Q000379:methods
chemical_list: D004146:Dioxanes; D009930:Organic Chemicals; D010758:Phosphorus; C076489:Meldrum's acid
keywords: kinetics; mechanism; stopped-flow; zwitterionic intermediate