Title
EPR investigation of <tex>$TiCl_{3}$</tex> dissolved in polar solvents : implications for the understanding of active Ti(III) species in heterogeneous Ziegler-Natta catalysts EPR investigation of <tex>$TiCl_{3}$</tex> dissolved in polar solvents : implications for the understanding of active Ti(III) species in heterogeneous Ziegler-Natta catalysts
Author
Faculty/Department
Faculty of Sciences. Physics
Publication type
article
Publication
Cambridge ,
Subject
Physics
Chemistry
Source (journal)
Physical chemistry, chemical physics / Chemical Society [London] - Cambridge, 1999, currens
Volume/pages
16(2014) :36 , p. 19625-19633
ISSN
1463-9076
ISI
000341299500064
Carrier
E
Target language
English (eng)
Full text (Publishers DOI)
Affiliation
University of Antwerp
Abstract
Multi-frequency continuous-wave and pulsed EPR techniques are employed to investigate Ti(III)-chloro complexes obtained by dissolving TiCl3 in anhydrous and hydrated methanol. Two distinctly different species, characterized by different g matrices are observed in the two cases. Hyperfine sublevel correlation (HYSCORE) spectroscopy is found to be a powerful method to identify the type of nuclei surrounding the Ti3+ ion. For the first time, the hyperfine and nuclear quadrupole data of Ti(m)-bound Cl-35/37 nuclei are reported together with H-1 and C-13 hyperfine data of the coordinated methanol molecules. DFT modelling allows interpreting the measured spin Hamiltonian parameters in terms of microscopic models of the solvated species. The theoretical observable properties (g matrix, Cl-35/37, H-1 and C-13 hyperfine tensors) are in quantitative agreement with the experiments for two families of complexes: [TiCln(CH3OH)(6-n)]((3-n)+) (with n ranging from 1 to 3) and [Ti(CH3OH)(5)(OH)](2+) or [Ti(CH3OH)(5)(OCH3)](2+). The first complex is observed in anhydrous methanol, while the second type of complex is observed when water is added to the solution, the presence of OH- and/or CH3O- species being promoted by water hydrolysis. The results obtained for the frozen solutions are critically compared to EPR spectra recorded for a MgCl2-supported Ti-based Ziegler-Natta model catalyst.
E-info
https://repository.uantwerpen.be/docman/iruaauth/e54914/9ca8481.pdf
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