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Cationic Palladium eta3-Allyl Complexes with Hemilabile P,O-Ligands : Synthesis and Reactivity, Insertion of Ethylene into the Pd-Allyl Function

Cationic Palladium eta3-Allyl Complexes with Hemilabile P,O-Ligands : Synthesis and Reactivity, Insertion of Ethylene into the Pd-Allyl Function

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MECKING, Stefan, Wilhelm KEIM, 1996. Cationic Palladium eta3-Allyl Complexes with Hemilabile P,O-Ligands : Synthesis and Reactivity, Insertion of Ethylene into the Pd-Allyl Function. In: Organometallics. 15(11), pp. 2650-2656. ISSN 0276-7333. eISSN 1520-6041

@article{Mecking1996Catio-9541, title={Cationic Palladium eta3-Allyl Complexes with Hemilabile P,O-Ligands : Synthesis and Reactivity, Insertion of Ethylene into the Pd-Allyl Function}, year={1996}, doi={10.1021/om960061z}, number={11}, volume={15}, issn={0276-7333}, journal={Organometallics}, pages={2650--2656}, author={Mecking, Stefan and Keim, Wilhelm} }

<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/123456789/9541"> <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2011-03-24T18:12:37Z</dc:date> <dcterms:rights rdf:resource="https://creativecommons.org/licenses/by-nc-nd/2.0/legalcode"/> <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/9541"/> <dc:contributor>Mecking, Stefan</dc:contributor> <dcterms:title>Cationic Palladium eta3-Allyl Complexes with Hemilabile P,O-Ligands : Synthesis and Reactivity, Insertion of Ethylene into the Pd-Allyl Function</dcterms:title> <dcterms:abstract xml:lang="eng">Cationic palladium allyl complexes [η3-C3H5)Pd(k2P^O)]+SbF6- (2[SbF6],P^O= Ph2P(CH2)2C-(=O)OEt; 3[SbF6], o-Ph2PC6H4C(=O)OEt; 4[SbF6], Ph2P(CH2)2P(=O)Ph2) have been prepared. In all complexes the oxygen donor can be displaced by other ligands such as carbon monoxide and ethylene. Displacement of an ester donor occurs much more readily than displacement of the phosphine oxide function. Above 0°C, the resulting ethylene complexes [η3-C3H5)Pd(C2H4)(k1P~O)]+ react to give (1,2,5-η3)-pent-1-en-5-yl complexes [(H2C=CH(CH2)3Pd(k2P^O)]+. A rate constant of e.g. k(17°C) = (2.27 ± 0.11) × 10-4 s-1 was determined for P,O ≡ Ph2P(CH2)2C(O)OEt by 1H NMR spectroscopy. Using 2-4 as catalyst precursors for ethylene dimerization, the allyl moiety is ultimately cleaved from the metal center as 1,4-pentadiene.</dcterms:abstract> <dcterms:bibliographicCitation>First publ. in: Organometallics ; 15 (1996), 11. - S. 2650-2656</dcterms:bibliographicCitation> <dc:contributor>Keim, Wilhelm</dc:contributor> <dc:format>application/pdf</dc:format> <dc:language>eng</dc:language> <dc:creator>Keim, Wilhelm</dc:creator> <dcterms:issued>1996</dcterms:issued> <dc:rights>deposit-license</dc:rights> <dc:creator>Mecking, Stefan</dc:creator> </rdf:Description> </rdf:RDF>

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