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

Brinkmann, Peter

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

Dateien

457_1.pdfGröße: 2.9 MBDownloads: 3078

Datum

1998

Autor:innen

Brinkmann, Peter

URI (zitierfähiger Link)

http://nbn-resolving.de/urn:nbn:de:bsz:352-opus-4578

Link zur Lizenz

Urheberrechtlich geschützt

Open Access-Veröffentlichung

Open Access Green

Sammlungen

Chemie

Titel in einer weiteren Sprache

CO-olefin copolymerization, a study on palladium(II) complexes with non-C2-symmetric ligands

Publikationstyp

Dissertation

Publikationsstatus

Published

Zusammenfassung

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.

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 ...

Zusammenfassung in einer weiteren Sprache

In dieser Arbeit wurden eine Reihe von P,N-Liganden dargestellt. Die Liganden haben eine C3-Brücke, wobei die Brücke Teil eines Aromaten ist. Am Phosphorzentrum wurden verschiedene Alkyl- und Arylsubstituenten eingeführt, das Stickstoffzentrum besteht aus e. substituierten Aminogruppe oder einem Pyridin-Stickstoff. Diese Liganden wurden zu Palladium(II)-Monomethylchlorid-Komplexen umgesetzt. Die Verbindungen wurden zu Triflat-Komplexen (Triflat = OSO2CF3) und zu kationischen P,N-PdMe+(L)(BArF)-Komplexen (L = CO, NCMe, BArF = (3,5-(CF3)2C6H3)4B) derivatisiert. Die erhaltenen P,N-Pd-Methylkomplexe wurden auf ihre Reaktivität gegenüber CO getestet. Die relativen CO-Insertionsraten der Alkylkomplexe wurden bestimmt. Weiter wurden die Reaktivitäten der Palladium-Acylkomplexe gegenüber 2-Norbornen getestet. Beide Monomere insertieren langsam in die Palladium-Kohlenstoffbindung. Für die Reaktionen der Alkylkomplexe mit Gemischen von 2-Norbornen und CO wurden hohe Geschwindigkeiten beobachtet. Die gewonnenen Ergebn. wurden im Rahmen eines allg. Modells interpretiert. Die unterschiedl. Reaktivitäten werden über das Auftreten reaktiver Intermediate erklärt, die schnellere Insertionsreaktionen ermöglichen als ihre thermodynamisch stabilen Isomere. Nach den gewonnenen Erkenntnissen läßt sich feststellen, daß P,N-Liganden für die Palladium(II)-katalysierte Copolymerisation von CO und a-Olefinen prinzipiell zu hohen Insertionsraten und damit zu hohen Katalysatoraktivitäten führen können.

Im 2. Teil d. Arbeit wurden neue, 2zähnige C2-verbrückte Pyridin-Imin-Liganden dargestellt. Der Pyridin- wie auch der Imin-Substituent wurden systematisch variiert. Diese Liganden wurden zu N,N'-Palladium-Alkylkomplexen umgesetzt, dazu neben literaturbekannten Umsetzungen neue Synthesen entwickelt. N,N'-Palladium-Alkylkomplexe wurden zum einen durch eine 'Eintopf'-Synthese des N,N'-PdCl2-Komplexes mit anschließender Monoalkylierung dargestellt, zum anderen durch e. Transalkylierung aus ...

Fachgebiet (DDC)

796 Sport

Schlagwörter

palladium, carbon monoxide, CO, 2-norbornene, alternating, styrene, oxidative, addition, N,N, P,N, bidentate, ligands

Zitieren

ISO 690

BRINKMANN, Peter, 1998. Untersuchungen zur CO/Olefin-Copolymerisation mit Hilfe von Palladium(II)-Komplexen mit nicht-C2-symmetrischen Liganden [Dissertation]. Konstanz: University of Konstanz

BibTex

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

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Prüfungsdatum der Dissertation

February 27, 1998