Accurate Experimental and Theoretical Enthalpies of Association of TiCl4 with Typical Lewis Bases Used in Heterogeneous Ziegler-Natta Catalysis
Type
ArticleAuthors
Credendino, RaffaeleMinenkov, Yury

Liguori, Dario
Piemontesi, Fabrizio
Melchior, Andrea
Morini, Giampiero
Tolazzi, Marilena
Cavallo, Luigi

KAUST Department
Chemical Science ProgramKAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Date
2017-09-18Permanent link to this record
http://hdl.handle.net/10754/625528
Metadata
Show full item recordAbstract
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.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.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.Publisher
Royal Society of Chemistry (RSC)Journal
Phys. Chem. Chem. Phys.PubMed ID
28956566Additional Links
http://pubs.rsc.org/en/Content/ArticleLanding/2017/CP/C7CP04047D#!divAbstracthttp://pubs.rsc.org/en/Content/ArticleLanding/2017/CP/C7CP04047D#!divAbstract
ae974a485f413a2113503eed53cd6c53
10.1039/c7cp04047d
Scopus Count
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