title: EPR investigation of TiCl3 dissolved in polar solvents--implications for the understanding of active Ti(III) species in heterogeneous Ziegler-Natta catalysts.
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 Ti(3+) ion. For the first time, the hyperfine and nuclear quadrupole data of Ti(III)-bound (35/37)Cl nuclei are reported together with (1)H and (13)C 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, (35/37)Cl, (1)H and (13)C 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.
authors.affiliation: University of Antwerp, Department of Physics, Universiteitsplein 1, B-2610 Wilrijk, Belgium. sabine.vandoorslaer@uantwerpen.be.
authors.forename: Sara
authors.initials: S
authors.lastname: Maurelli
authors.forename: Elena
authors.initials: E
authors.lastname: Morra
authors.forename: Sabine
authors.initials: S
authors.lastname: Van Doorslaer
authors.forename: Vincenzo
authors.initials: V
authors.lastname: Busico
authors.forename: Mario
authors.initials: M
authors.lastname: Chiesa