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

Angoy, Marta ; Jiménez, M. Victoria ; Vispe, Eugenio ; Podzimek, Stepan ; Pérez-Torrente, Jesús J. (Universidad de Zaragoza)

Resumen: 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.

Idioma: Inglés

DOI: 10.1039/d4py00497c

Año: 2024

Publicado en: POLYMER CHEMISTRY 30, 15 (2024), 3086-3099
ISSN: 1759-9954

Factor impacto JCR: 3.9 (2024)

Categ. JCR: POLYMER SCIENCE rank: 34 / 94 = 0.362 (2024) - Q2 - T2

Factor impacto SCIMAGO: 0.842 - Organic Chemistry (Q1) - Polymers and Plastics (Q1) - Bioengineering (Q2) - Biochemistry (Q2) - Biomedical Engineering (Q2)

Financiación: info:eu-repo/grantAgreement/ES/DGA/E42-23R
Financiación: info:eu-repo/grantAgreement/ES/MICINN-FEDER/PID2019-103965GB-I00
Financiación: info:eu-repo/grantAgreement/ES/MICINN/PID2022-137208NB-I00

Tipo y forma: Artículo (Versión definitiva)

Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)