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Catalysis design: from Ti-bis(enolato-imino) to Ti-bis(enolato-azo) in living olefin polymerization at DFT level

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Abstract

Reaction mechanisms of both propagation and termination steps in homogeneous polyolefin catalysis are investigated at DFT level. Starting from existent catalysts, we propose the design of a new Ti-bis(enolato-azo) catalytic family. We considered a number of hydrogenated or fluorinated models in aromatic group and chelating ring. Fluorination in the aromatic rings is able to control the propagation steps by activating the metal site, while hydrogenation of the ligand can inhibit the termination transfers. So, we have optimized the structure of the catalyst to give it the highest reactivity towards polymerization and the lowest one towards termination, by means of the meta-F substitutions in the aromatic group, and –CH2CF3 on the chelating ring. Thus, the developed bis(enolato-azo) models seem to be interesting for experimental investigations as new living catalysts.

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Authors and Affiliations

  1. Dipartimento di Scienze, Università degli Studi della Basilicata, Via dell’Ateneo Lucano 10, 85100, Potenza, Italy

    Gaetano Giammarino & Vincenzo Villani

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  1. Gaetano Giammarino
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  2. Vincenzo Villani
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Correspondence to Vincenzo Villani.

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Giammarino, G., Villani, V. Catalysis design: from Ti-bis(enolato-imino) to Ti-bis(enolato-azo) in living olefin polymerization at DFT level. Theor Chem Acc 135, 48 (2016). https://doi.org/10.1007/s00214-015-1804-6

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  • DOI: https://doi.org/10.1007/s00214-015-1804-6

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