Stereoregular polymerization of phenylacetylene using alkynyl and methyl rhodium(I) complexes with functionalized phosphine ligands: linear vs. branched poly(phenylacetylene)s

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216275%3A25310%2F24%3A39921803" target="_blank" >RIV/00216275:25310/24:39921803 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.rsc.org/en/Content/ArticleLanding/2024/PY/D4PY00497C" target="_blank" >https://pubs.rsc.org/en/Content/ArticleLanding/2024/PY/D4PY00497C</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d4py00497c" target="_blank" >10.1039/d4py00497c</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Stereoregular polymerization of phenylacetylene using alkynyl and methyl rhodium(I) complexes with functionalized phosphine ligands: linear vs. branched poly(phenylacetylene)s

Popis výsledku v původním jazyce

The alkynyl [Rh(C equivalent to C-Ph)(nbd){Ph2P(CH2)(3)Z}(2)] and [Rh(C equivalent to C-Ph)(cod){Ph2P(CH2)(3)Z}] (cod = 1,5-cyclooctadiene, nbd = 2,5-norbornadiene) and methyl complexes [Rh(CH3)(cod){Ph2P(CH2)(3)Z}] 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 equivalent to C-Ph)(cod){Ph2P(CH2)(3)Z}] having cod as the diene are linear, whereas the catalysts [Rh(C equivalent to C-Ph)(nbd){Ph2P(CH2)(3)Z}(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 equivalent to C-Ph)(nbd){Ph2P(CH2)(3)Z}(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 equivalent to C-Ph)(nbd)(PPh3)(2)] bearing a non-functionalized phosphine ligand and afford polymers with a much higher molecular weight.

Název v anglickém jazyce

Stereoregular polymerization of phenylacetylene using alkynyl and methyl rhodium(I) complexes with functionalized phosphine ligands: linear vs. branched poly(phenylacetylene)s

Popis výsledku anglicky

The alkynyl [Rh(C equivalent to C-Ph)(nbd){Ph2P(CH2)(3)Z}(2)] and [Rh(C equivalent to C-Ph)(cod){Ph2P(CH2)(3)Z}] (cod = 1,5-cyclooctadiene, nbd = 2,5-norbornadiene) and methyl complexes [Rh(CH3)(cod){Ph2P(CH2)(3)Z}] 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 equivalent to C-Ph)(cod){Ph2P(CH2)(3)Z}] having cod as the diene are linear, whereas the catalysts [Rh(C equivalent to C-Ph)(nbd){Ph2P(CH2)(3)Z}(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 equivalent to C-Ph)(nbd){Ph2P(CH2)(3)Z}(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 equivalent to C-Ph)(nbd)(PPh3)(2)] bearing a non-functionalized phosphine ligand and afford polymers with a much higher molecular weight.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10404 - Polymer science

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2024

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Polymer Chemistry

ISSN

1759-9954

e-ISSN

1759-9962

Svazek periodika

15

Číslo periodika v rámci svazku

30

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

14

Strana od-do

3086-3099

Kód UT WoS článku

001267511900001

EID výsledku v databázi Scopus

2-s2.0-85198969880