The typical activation of a fourth generation Ziegler-Natta catalyst TiCl4/MgCl2/phthalate with triethyl aluminum generates Ti(3+) centers that are investigated by multi-frequency continuous wave and pulse EPR methods. Two families of isolated, molecule-like Ti(3+) species have been identified. A comparison of the experimentally derived g tensors and (35,37)Cl hyperfine and nuclear-quadrupole tensors with DFT-computed values suggests that the dominant EPR-active Ti(3+)  species is located on MgCl2(110) surfaces (or equivalent MgCl2 terminations with tetra-coordinated Mg). O2 reactivity tests show that a fraction of these Ti sites is chemically accessible, an important result in view of the search for the true catalyst active site in olefin polymerization.

Probing the coordinative unsaturation and local environment of Ti³⁺ sites in an activated high-yield Ziegler-Natta catalyst / Morra, Elena; Giamello, Elio; Van Doorslaer, Sabine; Antinucci, Giuseppe; D'Amore, Maddalena; Busico, Vincenzo; Chiesa, Mario. - In: ANGEWANDTE CHEMIE. INTERNATIONAL EDITION. - ISSN 1433-7851. - 54:16(2015), pp. 4857-60-4860. [10.1002/anie.201412052]

Probing the coordinative unsaturation and local environment of Ti³⁺ sites in an activated high-yield Ziegler-Natta catalyst

ANTINUCCI, GIUSEPPE;D'AMORE, MADDALENA;BUSICO, VINCENZO;
2015

Abstract

The typical activation of a fourth generation Ziegler-Natta catalyst TiCl4/MgCl2/phthalate with triethyl aluminum generates Ti(3+) centers that are investigated by multi-frequency continuous wave and pulse EPR methods. Two families of isolated, molecule-like Ti(3+) species have been identified. A comparison of the experimentally derived g tensors and (35,37)Cl hyperfine and nuclear-quadrupole tensors with DFT-computed values suggests that the dominant EPR-active Ti(3+)  species is located on MgCl2(110) surfaces (or equivalent MgCl2 terminations with tetra-coordinated Mg). O2 reactivity tests show that a fraction of these Ti sites is chemically accessible, an important result in view of the search for the true catalyst active site in olefin polymerization.
2015
Probing the coordinative unsaturation and local environment of Ti³⁺ sites in an activated high-yield Ziegler-Natta catalyst / Morra, Elena; Giamello, Elio; Van Doorslaer, Sabine; Antinucci, Giuseppe; D'Amore, Maddalena; Busico, Vincenzo; Chiesa, Mario. - In: ANGEWANDTE CHEMIE. INTERNATIONAL EDITION. - ISSN 1433-7851. - 54:16(2015), pp. 4857-60-4860. [10.1002/anie.201412052]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11588/636111
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