000136346 001__ 136346
000136346 005__ 20250923084419.0
000136346 0247_ $$2doi$$a10.1039/d4py00497c
000136346 0248_ $$2sideral$$a139252
000136346 037__ $$aART-2024-139252
000136346 041__ $$aeng
000136346 100__ $$aAngoy, Marta
000136346 245__ $$aStereoregular polymerization of phenylacetylene using alkynyl and methyl rhodium(<scp>i</scp>) complexes with functionalized phosphine ligands: linear <i>vs.</i> branched poly(phenylacetylene)s
000136346 260__ $$c2024
000136346 5060_ $$aAccess copy available to the general public$$fUnrestricted
000136346 5203_ $$aThe 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.
000136346 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E42-23R$$9info:eu-repo/grantAgreement/ES/MICINN-FEDER/PID2019-103965GB-I00$$9info:eu-repo/grantAgreement/ES/MICINN/PID2022-137208NB-I00
000136346 540__ $$9info:eu-repo/semantics/openAccess$$aby-nc$$uhttp://creativecommons.org/licenses/by-nc/3.0/es/
000136346 590__ $$a3.9$$b2024
000136346 592__ $$a0.842$$b2024
000136346 591__ $$aPOLYMER SCIENCE$$b34 / 94 = 0.362$$c2024$$dQ2$$eT2
000136346 593__ $$aOrganic Chemistry$$c2024$$dQ1
000136346 593__ $$aPolymers and Plastics$$c2024$$dQ1
000136346 593__ $$aBioengineering$$c2024$$dQ2
000136346 593__ $$aBiochemistry$$c2024$$dQ2
000136346 593__ $$aBiomedical Engineering$$c2024$$dQ2
000136346 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000136346 700__ $$aJiménez, M. Victoria
000136346 700__ $$0(orcid)0000-0002-4921-4734$$aVispe, Eugenio
000136346 700__ $$aPodzimek, Stepan
000136346 700__ $$0(orcid)0000-0002-3327-0918$$aPérez-Torrente, Jesús J.$$uUniversidad de Zaragoza
000136346 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000136346 773__ $$g30, 15 (2024), 3086-3099$$pPOLYMER CHEMISTRY$$tPOLYMER CHEMISTRY$$x1759-9954
000136346 8564_ $$s1555902$$uhttps://zaguan.unizar.es/record/136346/files/texto_completo.pdf$$yVersión publicada
000136346 8564_ $$s2755422$$uhttps://zaguan.unizar.es/record/136346/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000136346 909CO $$ooai:zaguan.unizar.es:136346$$particulos$$pdriver
000136346 951__ $$a2025-09-22-14:35:01
000136346 980__ $$aARTICLE