Ruthenium- und Cobalt-basierte Funktionsmoleküle für die Metallabscheidung aus der Gasphase und Redoxcarbonylierung von Nitroaromaten

Die Arbeit gliedert sich in zwei inhaltlich unabhängige Kapitel, wobei das erste das umfangreichere ist. Gegenstand dieses ersten Kapitels war die Synthese, Charakterisierung und thermische Untersuchung flüchtiger Metallverbindungen, welche als potentielle Präkursoren in Prozessen der chemischen Ga...

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Bibliographic Details
Main Author: Schumann, Henrik
Contributors: Sundermeyer, Jörg (Prof. Dr.) (Thesis advisor)
Format: Doctoral Thesis
Published: Philipps-Universität Marburg 2019
Online Access:PDF Full Text
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Table of Contents: The first chapter of this thesis deals with the synthesis, characterization and the investigation of the thermal behavior of volatile transition metal complexes, which were discussed as precursors for chemical vapour deposition (CVD). The research activity focused on ruthenium and cobalt complexes. All target compounds based on the structural motive of N-donor ligands, e.g. amidinates, guanidinates or 1,4-diazadiens. Further, heteroleptic ruthenium complexes were combined with carbonyl, cyclopentadienyl or arene ligands. Thermoanalytical characterization of comparable compounds was done for better understandig the correlation between the thermal behavior and the molecular design. For example a correlation between complexes with ligands incorporating further N-N bonds and a decomposition at lower temperatures was determined. All complexes should have a melting point at low temperature and a defined decomposition temperature as well as a broad temperature range for a decomposition-free vaporization. A great amount of volatile ruthenium and cobalt complexes with such low melting points and broad temperature ranges for decomposition-free vaporization were obtained. As well, at room temperature liquid ruthenium complexes could be synthesized, which showed promising rates of vaporization. The secound chapter deals with the synthesis and characterization of cobalt complexes incorporation salen-like ligands, which were discussed as catalysts in the redoxcarbonylation of nitrobenzene and aniline in the presence of methanol. Regarding the strucutral motive of the salene ligand, variations of the diamino and/or the aldehyde precursor led to several chelate ligands and their cobalt complexes. The catalytic activities of them were investigated with respect to the development of a phosgene-free synthesis of polyurethanes.