126411 20241125101137.0 doi 10.1016/j.eurpolymj.2023.112117 sideral 133819 ART-2023-133819 eng Hermosilla, Pablo (orcid)0000-0003-2249-6054 Tailor-made poly(vinylidene sulfide)s by Rh(I)–NHC catalyzed regioselective thiol-yne click polymerization 2023 Access copy available to the general public Unrestricted The [Rh(μ-Cl)(IPr)(η2-coe)]2/pyridine system efficiently catalyzes the polyhydrothiolation of a series of dialkynes with dithiols, producing sulfur-rich poly(vinylidene sulfide)s with a typical Mw in the range 20.000–124.000 and vinylidene content of 75–87%. A combination of flexible aliphatic dithiols, including 1,6-hexanedithiol and 2,2′-(ethylendioxy)diethanethiol, and the rigid aromatic dithiol 4,4′-thiobisbenzenethiol, with rigid aromatic dialkynes, 1,3-diethynylbenzene and 1,4-diethynylbenzene, and flexible dialkynes, including propargyl ether and 1,7-octadiyne, have been used to prepare poly(vinylidene sulfide)s. The copolymerization of flexible dithiols with rigid aromatic dialkynes or vice versa results in high molecular weight polymers, Mw up to 259.000, with low polydispersities. However, polyhidrothiolation of flexible dialkynes with flexible dithiols is much less efficient and usually results in the formation of oligomers. The interplay of the IPr and pyridine ligands on the RhCl(IPr)(py)(η2-coe) catalyst, which controls the regioselectivity of the alkyne insertion step towards the branched vinyl sulfide, is key in the preparation of these poly(vinylidene sulfide)s. info:eu-repo/grantAgreement/ES/DGA-FSE/E42-20R info:eu-repo/grantAgreement/ES/MICINN/PID2019-103965GB-I00/AEI/10.13039/501100011033 info:eu-repo/semantics/openAccess by-nc-nd http://creativecommons.org/licenses/by-nc-nd/3.0/es/ 5.8 2023 POLYMER SCIENCE 9 / 95 = 0.095 2023 Q1 T1 0.982 2023 Materials Chemistry 2023 Q1 Polymers and Plastics 2023 Q1 Physics and Astronomy (miscellaneous) 2023 Q1 Organic Chemistry 2023 Q1 9.9 2023 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Funes-Hernando, Daniel Castarlenas, Ricardo (orcid)0000-0003-4460-8678 Di Giuseppe, Andrea Azpíroz, Ramón Vispe, Eugenio (orcid)0000-0002-4921-4734 Pérez-Torrente, Jesús J. Universidad de Zaragoza (orcid)0000-0002-3327-0918 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 194 (2023), 112117 [10 pp] Eur. Polym. J. European Polymer Journal 0014-3057 3153174 http://zaguan.unizar.es/record/126411/files/texto_completo.pdf Versión publicada 2653134 http://zaguan.unizar.es/record/126411/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:126411 articulos driver 2024-11-22-12:01:10 ARTICLE