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Untersuchungen zur CO/Olefin-Copolymerisation mit Hilfe von Palladium(II)-Komplexen mit nicht-C2-symmetrischen Liganden

Untersuchungen zur CO/Olefin-Copolymerisation mit Hilfe von Palladium(II)-Komplexen mit nicht-C2-symmetrischen Liganden

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BRINKMANN, Peter, 1998. Untersuchungen zur CO/Olefin-Copolymerisation mit Hilfe von Palladium(II)-Komplexen mit nicht-C2-symmetrischen Liganden

@phdthesis{Brinkmann1998Unter-9795, title={Untersuchungen zur CO/Olefin-Copolymerisation mit Hilfe von Palladium(II)-Komplexen mit nicht-C2-symmetrischen Liganden}, year={1998}, author={Brinkmann, Peter}, address={Konstanz}, school={Universität Konstanz} }

1998 Untersuchungen zur CO/Olefin-Copolymerisation mit Hilfe von Palladium(II)-Komplexen mit nicht-C2-symmetrischen Liganden Brinkmann, Peter application/pdf In this thesis, the synthesis of various P,N-ligands is reported. The ligands contain a C3-bridge that is part of an aromatic system. The phosphorus atom contains alkyl and/or aryl substituents, the nitrogen donor is provided by a trialkyl substituted nitrogen or a pyridine entity. The P,N-ligands were reacted with a suitable palladium precursor to yield (P,N)-palladium monomethyl chloride complexes. The latter were derivatized to triflate (triflate = OSO2CF3) and cationic P,N-PdMe+(L)(BArF) analogs (L = CO, NCMe, BArF = (3,5-(CF3)2C6H3)4B). The P,N-Pd methyl complexes were screened for their reactivity toward carbon monoxide. The relative insertion rates of the alkyl complexes were determined. In addition, the reactivity of the Pd-acyl compounds toward 2-norbornene was examined. Both monomers insert slowly into the palladium carbon bond. In contrast, the reaction of the alkyl complexes with a mixture of 2-norbornene and CO is fast, although the same product is formed as result of a consecutive insertion of CO and norbornene into a palladium carbon bond. The different insertion rate for consecutive vs. simultaneous addition of the monomers is explained through the presence of reactive intermediates that allow higher insertion rates than their isomerized, thermodynamically stable congeners. It led to the conclusion, that under certain circumstances, palladium catalysts with P,N ligands may constitute highly active catalysts for the copolymerization of CO and a-olefines.<br /><br />In the second part new bidentate C2-bridged pyridine-imine ligands are described. Both pyridine and imine parts were systematically derivatized. The array of ligands were transformed into N,N'-palladium alkyl complexes. New syntheses were developed for this purpose, e.g. N,N'-palladium alkyl complexes were obtained in a one pot procedure starting from N,N'-PdCl2 and subsequent monoalkylation, or by transalkylation of N,N'-PdCl2 with (TMEDA)PdMe2, or, by the oxidative addition of alkyl halides ... deposit-license 2011-03-24T18:14:27Z CO-olefin copolymerization, a study on palladium(II) complexes with non-C2-symmetric ligands Brinkmann, Peter 2011-03-24T18:14:27Z deu

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