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Novel Strategies for the Synthesis of Tungsten(VI) and Molybdenum(VI) Imido/Oxo Alkylidene NHC Complexes and Their Application in Ring-Opening Metathesis Polymerization

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Novel Strategies for the Synthesis of Tungsten(VI) and Molybdenum(VI) Imido/Oxo Alkylidene NHC Complexes and Their Application in Ring-Opening Metathesis Polymerization (Tienda española)

Janis Musso (Autor)


Lectura de prueba, PDF (520 KB)
Indice, PDF (120 KB)

ISBN-13 (Impresion) 9783736976115
ISBN-13 (E-Book) 9783736966116
Idioma Inglés
Numero de paginas 186
Laminacion de la cubierta mate
Edicion 1.
Lugar de publicacion Göttingen
Lugar de la disertacion Stuttgart
Fecha de publicacion 12.05.2022
Clasificacion simple Tesis doctoral
Area Química
Palabras claves Carbene, Molybdän, Wolfram, N-Heterocyclisch, organometallisch, Polymerisation, ROMP, Metathese, Ringöffnung, Komplexe, Imido, Oxo, Alkyliden, latent, Übergangsmetall, Schrock, Olefin, Grubbs, Pyrrolid, Bispyrrolid, Alkoxid, Alkyl, alpha-H, Abstraktion, Katalyse, Dicyclopentadien, DCPD, NHC, Norbornen, stereospezifisch, Isocyanat, Borat, selektiv, chelatisierend, Aryloxid, Cycloaddition, Synthese, kinetischer Isotopeneffekt, KIE, dynamische Differenzkaloriemetrie, DSC, Ligand, Triflat, carbenes, molybdenum, tungsten, N-heterocyclic, organometallics, polymerization, ROMP, metathesis, ring-opening, complexes, imido, oxo, alkylidene, latent, transition metal, Schrock, olefin, Grubbs, pyrrolide, bispyrrolide, alkoxide, alkyl, alpha-H, abstraction, catalysis, dicyclopentadiene, DCPD, NHC, norbornene, stereospecific, isocyanate, borate, selective, chelating, aryloxide, cycloaddition, synthesis, kinetic isotope effect, KIE, differential scanning calorimetry, DSC, ligand, triflate
URL para pagina web externa https://www.ipoc.uni-stuttgart.de/msf/team/Musso/

Recently, the synthesis of neutral and cationic group(VI) imido/oxo alkylidene N-heterocyclic carbene (NHC) complexes that tolerate protic functional groups and aldehydes was reported. Unprecedented turnover numbers of up to 1.2 million were found for their silica-supported representatives. Some group(VI) alkylidene NHC complexes even display stability towards moisture and air. Coordination of the NHC to tungsten imido bistriflate precursor complexes, however, can lead to undesired side reactions. This work consequently aimed at the development of novel, more efficient routes to neutral and cationic tungsten imido/oxo alkylidene NHC complexes. In addition, some molybdenum imido alkylidene NHC complexes were targeted. Thereby, the scope of synthetically accessible complexes was broadened and, subsequently, their reactivity in ring-opening metathesis polymerization (ROMP) was probed. Those complexes were used as thermally latent initiators for the ROMP of dicyclopentadiene. Precise determination of the onset temperature of polymerization was achieved via monitoring with differential scanning calorimetry. Furthermore, the selectivity of novel complexes was tested for the formation of stereoregular polymers through ROMP of enantiomerically pure norbornene derivatives, which allowed for the synthesis of up to 98% trans-isotactic or cis-syndiotactic polymers depending on the steric demand of the imido and the alkoxide ligand.