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Übergangsmetallkomplexe eines stabilen Silylens

Übergangsmetallkomplexe eines stabilen Silylens

          
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About the Book

Das im Jahr 2006 entwickelte Diketiminatosilylen zeigt aufgrund seiner zwitterionischen Struktur im Gegensatz zu "gewöhnlichen" Silylenen eine bemerkenswerte Reaktivität. Neben den beiden reaktiven Funktionen am Siliciumzentrum verfügt das Diketiminatosilylen über eine zusätzliche Donorfunktion im Ligandenrückgrat. Ziel dieser Doktorarbeit ist es, die Reaktivität und katalytische Aktivität des ?-Diketiminatosilylens und dabei insbesondere dessen Eigenschaften als Ligand in Übergangsmetallkomplexen zu untersuchen. Die Umsetzung des Silylens mit Arsan liefert beispielsweise durch eine doppelte As-H-Bindungsaktivierung ein donorstabilisiertes Arsasilen mit einer einzigartigen HSi=AsH-Einheit. Die Reaktion des Silylens mit Ammin als Wasserstoffquelle verläuft hingegen zum thermodynamisch stabilen 1,1-Additionsprodukt. Durch gezielte Koordination des Silylens an ein Nickelzentrum lässt sich die Donorfunktion am Siliciumzentrum schützen. Die Wasserstoffaddition mit Aminboran erfolgt nun nur selektiv am Silylenliganden zu dem entsprechenden Hydridosilylen-Nickel-Komplex, während das Nickeltricarbonyl-Molekülfragment unangetastet bleibt. Der Si(II)hydrid-Komplex wird anschließend erfolgreich in Hydrosilylierungsreaktionen mit Alkinen ohne Zusatz eines exogenen Katalysators getestet. Die stöchiometrische Hydrosilylierung des Si(II)hydrids mit Diphenylacetylen liefert chemoselektiv das Hydrosilylierungsprodukt, dessen Alkenyleinheit cis-konfiguriert vorliegt. Es konnte gezeigt werden, dass das Nickeltricarbonyl-Fragment im Si(II)hydrid-Nickelkomplex nicht nur eine Schutzgruppenfunktion besitzt, sondern in der Hydrosilylierungsreaktion eine entscheidende Rolle spielt. Darüber hinaus wurde eine neue Methode für die Synthese neuartiger Übergangsmetallkomplexe, basierend auf dem Diketiminatosilylen, entwickelt. Da das freie Silylen mit den Chlor-verbrückten Dimerkomplexe unter milden Bedingungen keine Reaktion eingeht, wurde zunächst die Reaktion des Silylens mit HCl bei tiefen
About the Author: Miriam Stoelzel wurde 1984 in Berlin geboren. Ihr Interesse an Naturwissenschaften zeigte sich schon in der Schulzeit, weshalb sie beschloss ihr Abitur an der Lise-Meitner Schule, einem Oberstufenzentrum mit naturwissenschaftlicher Ausrichtung, zu absolvieren. Einen ersten Höhepunkt erreichte ihre junge Karriere bereits 2003 als sie den 1. Platz im Landeswettbewerb "Jugend forscht" gewann. Um ihr Interesse zu vertiefen, entschied sie sich, Chemie an der Westfälischen Wilhelms-Universität Münster zu studieren. Nach ihrem erfolgreichen Diplom kehrte sie nach Berlin zurück. Dort forschte sie in den folgenden Jahren an der Technischen Universität Berlin zum Thema "Übergangsmetallkomplexe eines stabilen Silylens".


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Product Details
  • ISBN-13: 9783954255788
  • Publisher: Disserta Verlag
  • Binding: Paperback
  • Language: German
  • Returnable: N
  • Weight: 217 gr
  • ISBN-10: 3954255782
  • Publisher Date: 08 Jul 2014
  • Height: 210 mm
  • No of Pages: 176
  • Spine Width: 10 mm
  • Width: 148 mm


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