Palladiumkomplexe sterisch gehinderter 1,3-Bis(arylimino)isoindoline - Synthese, Struktur und Reaktivität

Es wurde eine Reihe neuer Liganden des BAI-Typs dargestellt, darunter unsymmetrische, sterisch stark belastete sowie erstmals chirale. Die eingehend untersuchte Komplexierung der Liganden durch Palladium(II)-Ionen (insbesondere Palladiumacetat) führt zur Ausbildung von Komplexen in verschiedenen zum...

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Bibliographische Detailangaben
1. Verfasser: Kleeberg, Christian
Beteiligte: Bröring, Martin (Prof. Dr.) (BetreuerIn (Doktorarbeit))
Format: Dissertation
Sprache:Deutsch
Veröffentlicht: Philipps-Universität Marburg 2007
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A number of new ligands of the BAI type were prepared. Among them are unsymmetrical, sterically hindered as well as the first chiral ones. The complexation of these ligands by palladium(II) ions (especially palladium acetat) leads to the formation of complexes with different modes of coordination. Several of them have not been described previously. The synthesized complexes are thoroughly studied by structural and spectroscopical means as well as by investigating their reactivity. Especially intramolecular CH activation processes leading to cyclometallated complexes have been observed. The resulting material has likewise been characterized by structural and spectroscopical means. The kinetic of formation of one of these complexes is studied in detail and the parameters of activation are determined. Starting with one of these complexes (4-MeBTI)PdCl a plethora of cationic complexes of the type [(4-MeBTI)PdL]+ is synthesized. Comparing the structural properties of these complexes with analogous complexes of the tripyrrin ligand [(TrPy)PdL]+ the different coordination chemistry of both ligands is discussed in detail. Some of the synthesized palladium complexes are used as (pre-)catalysts in C=C hydrogenation and/or C-C cross-coupling reactions. While in principle an acceptable catalytic activity is observed, the results are indicative for a non-molecular catalysis.