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dc.contributor.authorCredendino, Raffaele
dc.contributor.authorMinenkov, Yury
dc.contributor.authorLiguori, Dario
dc.contributor.authorPiemontesi, Fabrizio
dc.contributor.authorMelchior, Andrea
dc.contributor.authorMorini, Giampiero
dc.contributor.authorTolazzi, Marilena
dc.contributor.authorCavallo, Luigi
dc.date.accessioned2017-10-02T10:53:15Z
dc.date.available2017-10-02T10:53:15Z
dc.date.issued2017-09-18
dc.identifier.citationCredendino R, Minenkov Y, Liguori D, Piemontesi F, Melchior A, et al. (2017) Accurate experimental and theoretical enthalpies of association of TiCl4 with typical Lewis bases used in heterogeneous Ziegler–Natta catalysis. Phys Chem Chem Phys. Available: http://dx.doi.org/10.1039/c7cp04047d.
dc.identifier.issn1463-9076
dc.identifier.issn1463-9084
dc.identifier.pmid28956566
dc.identifier.doi10.1039/c7cp04047d
dc.identifier.urihttp://hdl.handle.net/10754/625528
dc.description.abstractAdducts of TiCl4 with Lewis bases used as internal or external donors in heterogeneous Ziegler-Natta (ZN) catalysis represents a fundamental interaction contributing to the final composition of MgCl2 supported ZN-catalysts. This study presents the accurate experimental evaluation, from titration calorimetry, of the formation enthalpy of TiCl4 adducts with 15 Lewis bases of industrial interests. In addition, we report accurate energies of association of TiCl4 with the same Lewis bases from calculations at the DLPNO-CCSD(T) level of theory. These accurate experimental and theoretical association values are compared with selected methods based on density functional theory (DFT) in combination with popular continuum solvation models. Calculations suggest that the PBE-D3, and M06 functionals in combination with a triple-ζ plus polarization quality basis set provide the best performance when the basis set superposition error (BSSE) is not removed from the association energies. Cleaning the association energies by the BSSE with the counterpoise protocol suggests the B3LYP-D3, TPSS-D3 and M06L as the best performing functionals. Introducing solvent effects with the PCM and SMD continuum solvation models allows comparing the DFT based association enthalpies with the experimental values obtained from titration calorimetry. Both solvation models in combination with the PBE-D3, PBE0-D3, B3LYP-D3, TPSS-D3, M06L, and M06 functionals provide association enthalpies close to the experimental values with MUEs in range 10 – 15 kJ/mol.
dc.description.sponsorshipLC and YM thank the King Abdullah University of Science and technology for supporting this work. Computing resources used within this project have been provided by the KAUST Supercomputing Laboratory and by CRESCO/ENEAGRID High Performance Computing infrastructure and its staff.
dc.publisherRoyal Society of Chemistry (RSC)
dc.relation.urlhttp://pubs.rsc.org/en/Content/ArticleLanding/2017/CP/C7CP04047D#!divAbstract
dc.relation.urlhttp://pubs.rsc.org/en/Content/ArticleLanding/2017/CP/C7CP04047D#!divAbstract
dc.rightsArchived with thanks to Phys. Chem. Chem. Phys.
dc.titleAccurate Experimental and Theoretical Enthalpies of Association of TiCl4 with Typical Lewis Bases Used in Heterogeneous Ziegler-Natta Catalysis
dc.typeArticle
dc.contributor.departmentChemical Science Program
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalPhys. Chem. Chem. Phys.
dc.eprint.versionPost-print
dc.contributor.institutionBasell Italia Srl, G. Natta Research Center, Piazzale G. Donegani 12, 44100 Ferrara, Italy.
dc.contributor.institutionDipartimento Politecnico di Ingegneria e Architettura dell’Università di Udine, Laboratori di Scienze e Tecnologie Chimiche, via delle Scienze 99, 33100 Udine, Italy.
dc.contributor.institutionDipartimento Politecnico di Ingegneria e Architettura dell'Università di Udine, Laboratori di Scienze e Tecnologie Chimiche, via delle Scienze 99, 33100 Udine, Italy.
kaust.personCredendino, Raffaele
kaust.personCredendino, Raffaele
kaust.personMinenkov, Yury
kaust.personMinenkov, Yury
kaust.personCavallo, Luigi
kaust.personCavallo, Luigi
refterms.dateFOA2018-09-18T00:00:00Z


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