Savka, Roman (2014):
Synthesis and Application of New Ruthenium-Based Olefin Metathesis Catalysts.
TU Darmstadt,
[Ph.D. Thesis]
Abstract
A new hexahydro-s-indacene based NHC ligand and transition metal complexes with Ag, Ir and Ru were prepared. The catalytic behavior of ruthenium complexes with the new NHC ligand in ring-closing metathesis reactions of sterically demanding substrates was investigated. New N-Hoveyda-type and 2-aryloxy-substituted Hoveyda-type complexes were synthesized in the reaction of the Grubbs 3rd generation type complexes [RuCl2(NHC)(3-phenylindeneylidene)(Py)] (NHC = SIMes, SIPr) with 2-ethenyl-N-alkyl-N-phenylaniline (alkyl = Me, Et) and 1-ethenyl-2-phenoxybenzenes (with EWG/EDG groups R para to oxygen).The catalytic activity in various RCM reactions was probed and the new complexes found to be highly efficient. Eight new Hoveyda-type complexes with ferrocenyl substituents were synthesized. Two of these complexes were found to be latent catalysts for ROMP reactions in the reduced state, but are able to polymerize cis-cyclooctene following chemical or electrochemical oxidation of the ferrocenyl group.
| Item Type: |
Ph.D. Thesis
|
| Erschienen: |
2014 |
| Creators: |
Savka, Roman |
| Title: |
Synthesis and Application of New Ruthenium-Based Olefin Metathesis Catalysts |
| Language: |
English |
| Abstract: |
A new hexahydro-s-indacene based NHC ligand and transition metal complexes with Ag, Ir and Ru were prepared. The catalytic behavior of ruthenium complexes with the new NHC ligand in ring-closing metathesis reactions of sterically demanding substrates was investigated. New N-Hoveyda-type and 2-aryloxy-substituted Hoveyda-type complexes were synthesized in the reaction of the Grubbs 3rd generation type complexes [RuCl2(NHC)(3-phenylindeneylidene)(Py)] (NHC = SIMes, SIPr) with 2-ethenyl-N-alkyl-N-phenylaniline (alkyl = Me, Et) and 1-ethenyl-2-phenoxybenzenes (with EWG/EDG groups R para to oxygen).The catalytic activity in various RCM reactions was probed and the new complexes found to be highly efficient. Eight new Hoveyda-type complexes with ferrocenyl substituents were synthesized. Two of these complexes were found to be latent catalysts for ROMP reactions in the reduced state, but are able to polymerize cis-cyclooctene following chemical or electrochemical oxidation of the ferrocenyl group. |
| Divisions: |
07 Department of Chemistry > Fachgebiet Anorganische Chemie
07 Department of Chemistry |
| Date Deposited: |
18 May 2014 19:55 |
| URL / URN: |
http://tuprints.ulb.tu-darmstadt.de/3947 |
| URN: |
urn:nbn:de:tuda-tuprints-39475 |
| PPN: |
|
| Referees: |
Plenio, Prof. Dr. Herbert ; Reggelin, Prof. Dr. Michael ; Schneider, Prof. Dr. Jörg J. ; Schäfer, Prof. Dr. Rolf |
| Refereed / Verteidigung / mdl. Prüfung: |
12 May 2014 |
| Alternative keywords: |
| Alternative keywords | Language |
|---|
| Catalysis, metathesis, ruthenium, N-heterocyclic carbenes. | English |
|
| Alternative Abstract: |
| Alternative abstract | Language |
|---|
Es wurden ein neuer Hexahydro-s-indacen-basierter NHC-Ligand, sowie die dazugehӧrigen Übergangsmetallkomplexe mit Ag, Ir und Ru dargestellt. Das katalytische Verhalten der Hexahydro-s-indacen–basierten Rutheniumkomplexe wurde mittels Ringschlussmetathese-Reaktion (RCM), unter Verwendung sterisch anspruchsvoller Substrate, untersucht. Neue Verbindungen der N-Hoveyda-Klasse und 2-Aryloxy-substituierte Hoveyda-Komplexe wurden durch die Reaktion von Grubbs-Komplexen der dritten Generation [RuCl2(NHC)(Ind)(Py)] (NHC = SIMes, SIPr, IPr) mit 2-Ethenyl-N-alkyl-N-phenylanilin (Alkyl = Me, Et) erhalten und 1-Ethenyl-2-phenoxybenzenen (mit EWG/EDG Substituenten R para zum Sauerstoff) synthetisiert. Die katalytische Aktivität wurde in zahlreichen RCM-Reaktionen untersucht und die neuen Komplexe als hoch effizient erkannt. Acht neue Hoveyda-Komplexe mit ferrocentragenden Substituenten wurden synthetisiert. Zwei dieser Komplexe stellten im reduzierten Zustand latente Katalysatoren für ROMP Reaktionen dar. Durch chemische oder elektrochemische Oxidation der Ferroceneinheit am Katalysator konnte cis-Cycloocten polymerisiert werden. | German |
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