Accurate Experimental and Theoretical Enthalpies of Association of TiCl4 with Typical Lewis Bases Used in Heterogeneous Ziegler-Natta Catalysis

Handle URI:
http://hdl.handle.net/10754/625528
Title:
Accurate Experimental and Theoretical Enthalpies of Association of TiCl4 with Typical Lewis Bases Used in Heterogeneous Ziegler-Natta Catalysis
Authors:
Credendino, Raffaele; Minenkov, Yury; Liguori, Dario; Piemontesi, Fabrizio; Melchior, Andrea; Morini, Giampiero; Tolazzi, Marilena; Cavallo, Luigi ( 0000-0002-1398-338X )
Abstract:
Adducts 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.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
Citation:
Credendino 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.
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Phys. Chem. Chem. Phys.
Issue Date:
18-Sep-2017
DOI:
10.1039/c7cp04047d
Type:
Article
ISSN:
1463-9076; 1463-9084
Sponsors:
LC 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.
Additional Links:
http://pubs.rsc.org/en/Content/ArticleLanding/2017/CP/C7CP04047D#!divAbstract; http://pubs.rsc.org/en/Content/ArticleLanding/2017/CP/C7CP04047D#!divAbstract
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorCredendino, Raffaeleen
dc.contributor.authorMinenkov, Yuryen
dc.contributor.authorLiguori, Darioen
dc.contributor.authorPiemontesi, Fabrizioen
dc.contributor.authorMelchior, Andreaen
dc.contributor.authorMorini, Giampieroen
dc.contributor.authorTolazzi, Marilenaen
dc.contributor.authorCavallo, Luigien
dc.date.accessioned2017-10-02T10:53:15Z-
dc.date.available2017-10-02T10:53:15Z-
dc.date.issued2017-09-18en
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.en
dc.identifier.issn1463-9076en
dc.identifier.issn1463-9084en
dc.identifier.doi10.1039/c7cp04047den
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.en
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.en
dc.publisherRoyal Society of Chemistry (RSC)en
dc.relation.urlhttp://pubs.rsc.org/en/Content/ArticleLanding/2017/CP/C7CP04047D#!divAbstracten
dc.relation.urlhttp://pubs.rsc.org/en/Content/ArticleLanding/2017/CP/C7CP04047D#!divAbstracten
dc.rightsArchived with thanks to Phys. Chem. Chem. Phys.en
dc.titleAccurate Experimental and Theoretical Enthalpies of Association of TiCl4 with Typical Lewis Bases Used in Heterogeneous Ziegler-Natta Catalysisen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalPhys. Chem. Chem. Phys.en
dc.eprint.versionPost-printen
dc.contributor.institutionBasell Italia Srl, G. Natta Research Center, Piazzale G. Donegani 12, 44100 Ferrara, Italy.en
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.en
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.en
kaust.authorCredendino, Raffaeleen
kaust.authorCredendino, Raffaeleen
kaust.authorMinenkov, Yuryen
kaust.authorMinenkov, Yuryen
kaust.authorCavallo, Luigien
kaust.authorCavallo, Luigien
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