136346 20260217205543.0 doi 10.1039/d4py00497c sideral 139252 ART-2024-139252 eng Angoy, Marta Stereoregular polymerization of phenylacetylene using alkynyl and methyl rhodium(<scp>i</scp>) complexes with functionalized phosphine ligands: linear <i>vs.</i> branched poly(phenylacetylene)s 2024 Access copy available to the general public Unrestricted The alkynyl [Rh(C[triple bond, length as m-dash]C-Ph)(nbd){Ph2P(CH2)3Z}2] and [Rh(C[triple bond, length as m-dash]C-Ph)(cod){Ph2P(CH2)3Z}] (cod = 1,5-cyclooctadiene, nbd = 2,5-norbornadiene) and methyl complexes [Rh(CH3)(cod){Ph2P(CH2)3Z}] featuring functionalized phosphine ligands (Z = NMe2, OEt) have been prepared. These complexes efficiently catalyze the polymerization of phenylacetylene in the absence of a base to afford stereoregular poly(phenylacetylene)s with high molar masses. Polymer characterization by SEC-MALS and A4F-MALS revealed a bimodal molar mass distribution due to the presence of a high molar mass polymer fraction. The diene ligand in the alkynyl complexes influences the morphology of the polymers. The poly(phenylacetylene)s prepared with the square-planar alkynyl complexes [Rh(C[triple bond, length as m-dash]C-Ph)(cod){Ph2P(CH2)3Z}] having cod as the diene are linear, whereas the catalysts [Rh(C[triple bond, length as m-dash]C-Ph)(nbd){Ph2P(CH2)3Z}2] with nbd as the diene afford PPAs with a fraction of high molar mass branched polymer. However, neither the catalytic performance nor the PPA morphology is affected by the donor function of the functionalized phosphine ligand (–NMe2 or –OEt). The alkynyl complexes having nbd as the diene ligand, [Rh(C[triple bond, length as m-dash]C-Ph)(nbd){Ph2P(CH2)3Z}2], are much more active than the square-planar alkynyl and methyl complexes having cod as the diene. These catalysts polymerize phenylacetylene at a faster rate than the catalyst [Rh(C[triple bond, length as m-dash]C-Ph)(nbd)(PPh3)2] bearing a non-functionalized phosphine ligand and afford polymers with a much higher molecular weight. info:eu-repo/grantAgreement/ES/DGA/E42-23R info:eu-repo/grantAgreement/ES/MICINN-FEDER/PID2019-103965GB-I00 info:eu-repo/grantAgreement/ES/MICINN/PID2022-137208NB-I00 info:eu-repo/semantics/openAccess by-nc https://creativecommons.org/licenses/by-nc/4.0/deed.es 4.0 2024 POLYMER SCIENCE 32 / 94 = 0.34 2024 Q2 T2 0.842 2024 Organic Chemistry 2024 Q1 Polymers and Plastics 2024 Q1 Bioengineering 2024 Q2 Biochemistry 2024 Q2 Biomedical Engineering 2024 Q2 7.6 2024 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Jiménez, M. Victoria Vispe, Eugenio (orcid)0000-0002-4921-4734 Podzimek, Stepan Pérez-Torrente, Jesús J. Universidad de Zaragoza (orcid)0000-0002-3327-0918 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 30, 15 (2024), 3086-3099 POLYMER CHEMISTRY POLYMER CHEMISTRY 1759-9954 1555902 http://zaguan.unizar.es/record/136346/files/texto_completo.pdf Versión publicada 2755422 http://zaguan.unizar.es/record/136346/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:136346 articulos driver 2026-02-17-20:37:20 ARTICLE