Mechanistic insights into Polar Monomer insertion polymerization from Acrylamides

Friedberger, Tobias; Wucher, Philipp; Mecking, Stefan

Mechanistic insights into Polar Monomer insertion polymerization from Acrylamides

Dateien

Mecking_Mechanistic.pdfGröße: 8.9 MBDownloads: 758

Datum

2012

Open Access-Veröffentlichung

Open Access Green

Sammlungen

Chemie

Publikationstyp

Zeitschriftenartikel

Publikationsstatus

Published

Erschienen in

Journal of the American Chemical Society. 2012, 134(2), pp. 1010-1018. ISSN 0002-7863. eISSN 1520-5126. Available under: doi: 10.1021/ja207110u

Zusammenfassung

N-Isopropyl acrylamide (NIPAM), N,N-dimethyl acrylamide (DMAA), and 2-acetamidoethyl acrylate (AcAMEA) were copolymerized with ethylene employing [(P^O)PdMe(DMSO)] (1-DMSO; P^O = κ2-P,O-Ar2PC6H4SO2O with Ar = 2-MeOC6H4) as a catalyst precursor. Inhibition studies with nonpolymerizable polar additives show that reversible κ-O-coordination of free amide retards polymerization significantly. Retardation of polymerization increases in the order ethyl acetate methyl ethyl sulfone < acetonitrile < N,N-dimethylacetamide ≈ N-methylacetamide ≈ propionic acid < dimethylsulfoxide. Pseudo-first-order rate constants for the insertion into 1-DMSO were determined to increase in the order DMAA < AcAMEA < NIPAM < methyl acrylate. Exposure of 1-DMSO to NIPAM resulted in the formation of consecutive insertion products [(P^O)Pd(C6H11NO2)nMe] (n ≤ 3), as determined by electrospray ionization mass spectrometry. The solid-state structure of the methanol adduct of the 2,1-insertion product of NIPAM into 1-DMSO, [(P^O)Pd{η1-CH(CONHiPr)CH2CH3}(κ1-O-MeOD)] (2-MeOD), was determined by single crystal X-ray diffraction. Both 2,1- and 1,2-insertions of DMAA into the Pd–Me bond of a [(P^O)PdMe] fragment occur to afford a ca. 4:1 mixture of chelates [(P^O)Pd{κ2-C,O–C(CH2CH3)C(O)NMe2}] (3) and [(P^O)Pd{κ2-C,O–CH2C(CH3)C(O)NMe2}] (4). The four-membered chelate of 3 is opened by coordination of 2,6-lutidine (3 + 2,6-lutidine 3-LUT) with ΔH° = −41.8(10.5) kJ and ΔS° = −115(37) J mol–1 K–1.

Fachgebiet (DDC)

540 Chemie

Zitieren

ISO 690

FRIEDBERGER, Tobias, Philipp WUCHER, Stefan MECKING, 2012. Mechanistic insights into Polar Monomer insertion polymerization from Acrylamides. In: Journal of the American Chemical Society. 2012, 134(2), pp. 1010-1018. ISSN 0002-7863. eISSN 1520-5126. Available under: doi: 10.1021/ja207110u

BibTex

@article{Friedberger2012-01-18Mecha-19325,
  year={2012},
  doi={10.1021/ja207110u},
  title={Mechanistic insights into Polar Monomer insertion polymerization from Acrylamides},
  number={2},
  volume={134},
  issn={0002-7863},
  journal={Journal of the American Chemical Society},
  pages={1010--1018},
  author={Friedberger, Tobias and Wucher, Philipp and Mecking, Stefan}
}

RDF

<rdf:RDF
    xmlns:dcterms="http://purl.org/dc/terms/"
    xmlns:dc="http://purl.org/dc/elements/1.1/"
    xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#"
    xmlns:bibo="http://purl.org/ontology/bibo/"
    xmlns:dspace="http://digital-repositories.org/ontologies/dspace/0.1.0#"
    xmlns:foaf="http://xmlns.com/foaf/0.1/"
    xmlns:void="http://rdfs.org/ns/void#"
    xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > 
  <rdf:Description rdf:about="https://kops.uni-konstanz.de/server/rdf/resource/123456789/19325">
    <dspace:hasBitstream rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/19325/2/Mecking_Mechanistic.pdf"/>
    <dc:rights>terms-of-use</dc:rights>
    <dc:contributor>Mecking, Stefan</dc:contributor>
    <dcterms:title>Mechanistic insights into Polar Monomer insertion polymerization from Acrylamides</dcterms:title>
    <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dc:language>eng</dc:language>
    <dc:contributor>Wucher, Philipp</dc:contributor>
    <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2012-05-22T09:28:46Z</dc:date>
    <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/server/rdf/resource/123456789/29"/>
    <dcterms:hasPart rdf:resource="https://kops.uni-konstanz.de/bitstream/123456789/19325/2/Mecking_Mechanistic.pdf"/>
    <dcterms:bibliographicCitation>First publ. in: Journal of the American Chemical Society ; 134 (2012), 2. - pp. 1010-1018</dcterms:bibliographicCitation>
    <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/19325"/>
    <foaf:homepage rdf:resource="http://localhost:8080/"/>
    <dcterms:rights rdf:resource="https://rightsstatements.org/page/InC/1.0/"/>
    <dc:creator>Mecking, Stefan</dc:creator>
    <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/>
    <dc:creator>Friedberger, Tobias</dc:creator>
    <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-12-31T23:25:07Z</dcterms:available>
    <dcterms:abstract xml:lang="eng">N-Isopropyl acrylamide (NIPAM), N,N-dimethyl acrylamide (DMAA), and 2-acetamidoethyl acrylate (AcAMEA) were copolymerized with ethylene employing [(P^O)PdMe(DMSO)] (1-DMSO; P^O = κ2-P,O-Ar2PC6H4SO2O with Ar = 2-MeOC6H4) as a catalyst precursor. Inhibition studies with nonpolymerizable polar additives show that reversible κ-O-coordination of free amide retards polymerization significantly. Retardation of polymerization increases in the order ethyl acetate methyl ethyl sulfone &lt; acetonitrile &lt; N,N-dimethylacetamide ≈ N-methylacetamide ≈ propionic acid &lt; dimethylsulfoxide. Pseudo-first-order rate constants for the insertion into 1-DMSO were determined to increase in the order DMAA &lt; AcAMEA &lt; NIPAM &lt; methyl acrylate. Exposure of 1-DMSO to NIPAM resulted in the formation of consecutive insertion products [(P^O)Pd(C6H11NO2)nMe] (n ≤ 3), as determined by electrospray ionization mass spectrometry. The solid-state structure of the methanol adduct of the 2,1-insertion product of NIPAM into 1-DMSO, [(P^O)Pd{η1-CH(CONHiPr)CH2CH3}(κ1-O-MeOD)] (2-MeOD), was determined by single crystal X-ray diffraction. Both 2,1- and 1,2-insertions of DMAA into the Pd–Me bond of a [(P^O)PdMe] fragment occur to afford a ca. 4:1 mixture of chelates [(P^O)Pd{κ2-C,O–C(CH2CH3)C(O)NMe2}] (3) and [(P^O)Pd{κ2-C,O–CH2C(CH3)C(O)NMe2}] (4). The four-membered chelate of 3 is opened by coordination of 2,6-lutidine (3 + 2,6-lutidine 3-LUT) with ΔH° = −41.8(10.5) kJ and ΔS° = −115(37) J mol–1 K–1.</dcterms:abstract>
    <dc:contributor>Friedberger, Tobias</dc:contributor>
    <dc:creator>Wucher, Philipp</dc:creator>
    <dcterms:issued>2012-01-18</dcterms:issued>
  </rdf:Description>
</rdf:RDF>

Universitätsbibliographie

Ja