Pentafluorphenylamid-Liganden als Designkonzept für funktionale Metall-Lewis-Säuren der Elemente des p- und d-Blocks

Im ersten Teil dieser Arbeit wird eine neue Methode zur Synthese N-pentafluorphenylsubstituierter Arylamine vorgestellt. Das neue Verfahren ermöglicht eine leichte Funktionalisierung der Stickstoffatome primärer Arylmono- sowie Aryldiamine mit C6F5 Substituenten. Wie gezeigt wurde, ist die Substitut...

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Bibliographic Details
Main Author: Sorokin Denis
Contributors: Sundermeyer Jörg (Prof. Dr.) (Thesis advisor)
Format: Dissertation
Language:German
Published: Philipps-Universität Marburg 2006
Chemie
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Table of Contents: There was presented a general method for the synthesis of N pentafluorophenyl-substituted aryl amines in the first part of this work. The new method allows a direct funktionalization of primary aryl amines with C6F5-groups. As was shown, the usage of protecting groups is not necessary in the case of carbonyl- and bromine-substituted aryl amines. The second part of this work handles with a synthesis, chemical behaviour and structural characterisation of chelating pentafluorophenyl amides of the elements of p- and d-blocks. New amides of lithium, tin, zinc and aluminium were synthesized. Dimethylamido complexes of titanium and zirconium were obtained in the metathetical reaction between M(NMe2)4 (M= Ti, Zr) and synthesized pentafluorophenyl amines. Further functionalization of the dimethylamido complexes to the corresponding dichloro- and dimethyl derivatives lead to the thermal unstable compounds. Thermal mach more stable dibenzyl derivatives were obtained in the reaction between MBz4 (M= Ti, Zr) and pentafluorophenyl amines. Synthesized dibenzyl complexes were activated with BCF. NMR-spectra of the reaction mixtures proove the building of stable none-coordinated cation-anion pairs that were shown to be inactive in the polymerisation of ethene. There were a number of new decafluorodiphenylamides (DFDPA) of main group elements reported in the third part of this work. The strong electron deficient properties of the decafluorodiphenylamido group gives wide possibilities for a design of new strong Lewis acids. Therefore, coordinates Led (II) decafluorodiphenylamide one- or two toluene molecules. Zinc (II) decafluorodiphenylamide coordinates one hexamethyldisilazane molecule as a Lewis base. Aluminium tris-decafluorodiphenylamide has a very strong Lewis acidity and is able to abstract a fluoride ion from hexafluoroantimonates. Aluminium tris-decafluorodiphenylamide and corresponding none-coordinated anions were tested in the polymerisation of ethene. Aluminium tris-decafluorodiphenylamide was shown to be active with dimethylzirconocene and triisobuthylaluminium as a scavenger. The catalytic system was inactive at higher concentrations of triisobuthylaluminium because of ligand exchange. In the present work 46 new compounds were synthesized, 20 of them were characterized with X-ray analysis.