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Catalyst activity and selectivity in the isomerising alkoxycarbonylation of methyl oleate

Catalyst activity and selectivity in the isomerising alkoxycarbonylation of methyl oleate

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CHRISTL, Josefine, Philipp ROESLE, Florian STEMPFLE, Philipp WUCHER, Inigo GÖTTKER-SCHNETMANN, Gerhard MÜLLER, Stefan MECKING, 2013. Catalyst activity and selectivity in the isomerising alkoxycarbonylation of methyl oleate. In: Chemistry - A European Journal. 19(50), pp. 17131-17140. ISSN 0947-6539. eISSN 1521-3765

@article{Christl2013-12-09Catal-26597, title={Catalyst activity and selectivity in the isomerising alkoxycarbonylation of methyl oleate}, year={2013}, doi={10.1002/chem.201301124}, number={50}, volume={19}, issn={0947-6539}, journal={Chemistry - A European Journal}, pages={17131--17140}, author={Christl, Josefine and Roesle, Philipp and Stempfle, Florian and Wucher, Philipp and Göttker-Schnetmann, Inigo and Müller, Gerhard and Mecking, Stefan} }

<rdf:RDF xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#" xmlns:bibo="http://purl.org/ontology/bibo/" xmlns:dc="http://purl.org/dc/elements/1.1/" xmlns:dcterms="http://purl.org/dc/terms/" xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > <rdf:Description rdf:about="https://kops.uni-konstanz.de/rdf/resource/123456789/26597"> <dcterms:abstract>The synthesis of unsymmetrical diphosphine ligands (3a-g) with an o-tolyl backbone and tert-butyl, adamantyl, cyclohexyl and isopropyl substituents on the phosphorus moiety is described (1,2-(CH2PR2)(PR'2)C6H4; 3a: R=tBu, R'=tBu, 3b: R=tBu, R'=Cy, 3c: R=tBu, R'=iPr, 3d: R=Ad, R'=tBu, 3e: R=Ad, R'=Cy, 3f: R=Cy, R'=Cy, 3g: R=Ad, R'=Ad). The corresponding diphosphine-Pd(II) ditriflate complexes [(P^P)Pd(OTf)2] (5a-g) were prepared and structurally characterised by X-ray crystallography. These new complexes were studied as catalyst precursors in the isomerising methoxycarbonylation of methyl oleate, and were found to convert methyl oleate into the corresponding linear α,ω-diester (L) with 70-80% selectivity. The products of this catalytic reaction with the known [{1,2-(tBu2PCH2)2C6H4}Pd(OTf)2] complex (5h) were fully analysed, and revealed the formation of the linear α,ω-diester (L, 89.0%), the methyl-branched diester B1 (4.3%), the ethyl-branched diester B2 (1.0%), the propyl-branched diester B3 (0.6%) and all diesters from butyl- to hexadecyl-branched diesters B4-B16 (overall 4.8%) at 90 °C and 20 bar CO. The productivity of the catalytic conversion of methyl oleate with complexes 5a-g varied with the steric bulk of the alkyl substituent on the phosphorus. Ligands with more bulky groups, like tert-butyl or adamantyl (e.g., 5a, 5d, 5g), were more productive systems. The formation of the catalytically active hydride species [(P^P)Pd(H)(MeOH)](+) (6-MeOH) was investigated and observed directly for complexes 5a-e and 5g, respectively. These hydride species were isolated as the corresponding triphenylphosphine complexes (6-PPh3) and fully characterised, including by X-ray crystallography. The catalytic productivity of 6a-PPh3 was virtually identical to that of 5a, thereby confirming the efficient hydride formation of 5a under catalytic conditions.</dcterms:abstract> <dc:contributor>Wucher, Philipp</dc:contributor> <dc:contributor>Müller, Gerhard</dc:contributor> <dc:contributor>Stempfle, Florian</dc:contributor> <dcterms:title>Catalyst activity and selectivity in the isomerising alkoxycarbonylation of methyl oleate</dcterms:title> <dcterms:bibliographicCitation>Chemistry - a European journal ; 19 (2013), 50. - S. 17131–17140</dcterms:bibliographicCitation> <dc:rights>deposit-license</dc:rights> <dc:creator>Göttker-Schnetmann, Inigo</dc:creator> <dcterms:issued>2013-12-09</dcterms:issued> <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2014-03-10T14:09:43Z</dc:date> <dc:creator>Stempfle, Florian</dc:creator> <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/26597"/> <dc:language>eng</dc:language> <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2014-03-10T14:09:43Z</dcterms:available> <dc:creator>Müller, Gerhard</dc:creator> <dc:contributor>Göttker-Schnetmann, Inigo</dc:contributor> <dc:contributor>Roesle, Philipp</dc:contributor> <dc:creator>Roesle, Philipp</dc:creator> <dc:contributor>Christl, Josefine</dc:contributor> <dc:contributor>Mecking, Stefan</dc:contributor> <dcterms:rights rdf:resource="http://nbn-resolving.org/urn:nbn:de:bsz:352-20140905103605204-4002607-1"/> <dc:creator>Mecking, Stefan</dc:creator> <dc:creator>Christl, Josefine</dc:creator> <dc:creator>Wucher, Philipp</dc:creator> </rdf:Description> </rdf:RDF>

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