000121091 001__ 121091
000121091 005__ 20240319080957.0
000121091 0247_ $$2doi$$a10.1039/d1py01650d
000121091 0248_ $$2sideral$$a131640
000121091 037__ $$aART-2022-131640
000121091 041__ $$aeng
000121091 100__ $$aAngoy, Marta
000121091 245__ $$aPolymerization of phenylacetylene catalyzed by rhodium(<scp>i</scp>) complexes with <i>N</i>-functionalized N-heterocyclic carbene ligands
000121091 260__ $$c2022
000121091 5060_ $$aAccess copy available to the general public$$fUnrestricted
000121091 5203_ $$aA series of neutral [RhX(nbd)(κC-MeIm∩Z)] and cationic [Rh(nbd)(κ2C,N-MeIm∩Z)]+ (X = Cl, Br; MeIm = 3-methylimidazol-2-yliden-1-yl; ∩Z = N-functionalized wingtip; nbd = 2,5-norbornadiene) complexes featuring NHC ligands functionalized with a 1-aminopropyl, 3-dimethylaminopropyl, pyridin-2-ylmethyl, or quinolin-8-ylmethyl substituent have been prepared. These complexes efficiently catalyze the polymerization of phenylacetylene without base as a co-catalyst affording stereoregular polyphenylacetylenes of very high molar mass. Polymers of Mw up to 2 × 106 g mol−1 and moderate dispersity have been prepared with neutral chloro-complexes having aminopropyl wingtips. Catalyst precursors bearing functionalized NHC ligands with a flexible amino-alkyl wingtip are significantly more active than those having a heterocyclic substituent. These complexes are in general much more active than related compounds having N-functionalized phosphine ligands. Polymer characterization by SEC/MALS/DRI analysis has revealed the presence of a fraction of branched polymer of high molar mass in most samples obtained with catalysts having N-heterocyclic substituents at the NHC ligand. The N-donor function at the NHC ligand likely behaves as an internal base for the deprotonation of phenylacetylene to give the initiating alkynyl cationic [Rh(nbd)(C[triple bond, length as m-dash]C-Ph)(κC-MeIm∩ZH)]+ species. However, the participation of neutral alkynyl species [Rh(nbd)(C[triple bond, length as m-dash]C-Ph)(κC-MeIm∩Z)] should be considered in order to rationalize the notable catalytic activity of some neutral chloro-complexes.
000121091 536__ $$9info:eu-repo/grantAgreement/ES/DGA-FSE/E42-20R$$9info:eu-repo/grantAgreement/ES/MICINN/PID2019-103965GB-I00/AEI/10.13039/501100011033
000121091 540__ $$9info:eu-repo/semantics/openAccess$$aby-nc$$uhttp://creativecommons.org/licenses/by-nc/3.0/es/
000121091 590__ $$a4.6$$b2022
000121091 592__ $$a1.014$$b2022
000121091 591__ $$aPOLYMER SCIENCE$$b18 / 85 = 0.212$$c2022$$dQ1$$eT1
000121091 593__ $$aBiomedical Engineering$$c2022$$dQ1
000121091 593__ $$aBioengineering$$c2022$$dQ1
000121091 593__ $$aPolymers and Plastics$$c2022$$dQ1
000121091 593__ $$aOrganic Chemistry$$c2022$$dQ1
000121091 593__ $$aBiochemistry$$c2022$$dQ2
000121091 594__ $$a8.6$$b2022
000121091 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000121091 700__ $$0(orcid)0000-0002-0545-9107$$aJiménez, M. Victoria
000121091 700__ $$aLahoz, Fernando J.
000121091 700__ $$0(orcid)0000-0002-4921-4734$$aVispe, Eugenio
000121091 700__ $$0(orcid)0000-0002-3327-0918$$aPérez-Torrente, Jesús J.$$uUniversidad de Zaragoza
000121091 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000121091 773__ $$g13, 10 (2022), 1411-1421$$pPOLYMER CHEMISTRY$$tPOLYMER CHEMISTRY$$x1759-9954
000121091 8564_ $$s2267449$$uhttps://zaguan.unizar.es/record/121091/files/texto_completo.pdf$$yVersión publicada
000121091 8564_ $$s2888335$$uhttps://zaguan.unizar.es/record/121091/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000121091 909CO $$ooai:zaguan.unizar.es:121091$$particulos$$pdriver
000121091 951__ $$a2024-03-18-13:41:45
000121091 980__ $$aARTICLE