title: A DFT-Based Computational-Experimental Methodology for Synthetic Chemistry: Example of Application to the Catalytic Opening of Epoxides by Titanocene.
abstract: A novel DFT-based Reaction Kinetics (DFT-RK) simulation approach, employed in combination with real-time data from reaction monitoring instrumentation (like UV-vis, FTIR, Raman, and 2D NMR benchtop spectrometers), is shown to provide a detailed methodology for the analysis and design of complex synthetic chemistry schemes. As an example, it is applied to the opening of epoxides by titanocene in THF, a catalytic system with abundant experimental data available. Through a DFT-RK analysis of real-time IR data, we have developed a comprehensive mechanistic model that opens new perspectives to understand previous experiments. Although derived specifically from the opening of epoxides, the prediction capabilities of the model, built on elementary reactions, together with its practical side (reaction kinetics simulations of real experimental conditions) make it a useful simulation tool for the design of new experiments, as well as for the conception and development of improved versions of the reagents. From the perspective of the methodology employed, because both the computational (DFT-RK) and the experimental (spectroscopic data) components can follow the time evolution of several species simultaneously, it is expected to provide a helpful tool for the study of complex systems in synthetic chemistry.
authors.affiliation: Department of Electronics, ETSIT, University of Valladolid , Paseo Belén 15, Valladolid 47011, Spain.
authors.forename: Martín
authors.identifier: 0000-0001-6688-3158
authors.initials: M
authors.lastname: Jaraíz
authors.affiliation: Department of Electronics, ETSIT, University of Valladolid , Paseo Belén 15, Valladolid 47011, Spain.
authors.forename: Lourdes
authors.initials: L
authors.lastname: Enríquez
authors.affiliation: Department of Electronics, ETSIT, University of Valladolid , Paseo Belén 15, Valladolid 47011, Spain.
authors.forename: Ruth
authors.initials: R
authors.lastname: Pinacho
authors.affiliation: Department of Electronics, ETSIT, University of Valladolid , Paseo Belén 15, Valladolid 47011, Spain.
authors.forename: José E
authors.initials: JE
authors.lastname: Rubio
authors.affiliation: Department of Physical Chemistry and Inorganic Chemistry, Faculty of Sciences, University of Valladolid , Paseo Belén 7, Valladolid 47011, Spain.
authors.forename: Alberto
authors.identifier: 0000-0002-0646-6341
authors.initials: A
authors.lastname: Lesarri
authors.affiliation: Department of Pharmaceutical Sciences - IBSAL-CIETUS, University of Salamanca , Avda. Campo Charro s/n, Salamanca 37071, Spain.|Department of Pharmacology, Faculty of Medicine, University of Panama , Panama City, Panama.
authors.forename: José L
authors.initials: JL
authors.lastname: López-Pérez