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http://dx.doi.org/10.18419/opus-13513
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DC Element | Wert | Sprache |
---|---|---|
dc.contributor.author | Buchmeiser, Michael R. | - |
dc.contributor.author | Probst, Patrick | - |
dc.contributor.author | Wang, Dongren | - |
dc.contributor.author | Hauser, Philipp | - |
dc.date.accessioned | 2023-09-15T09:47:04Z | - |
dc.date.available | 2023-09-15T09:47:04Z | - |
dc.date.issued | 2022 | de |
dc.identifier.issn | 1521-3935 | - |
dc.identifier.other | 1860433960 | - |
dc.identifier.uri | http://nbn-resolving.de/urn:nbn:de:bsz:93-opus-ds-135327 | de |
dc.identifier.uri | http://elib.uni-stuttgart.de/handle/11682/13532 | - |
dc.identifier.uri | http://dx.doi.org/10.18419/opus-13513 | - |
dc.description.abstract | A series of cationic tungsten sulfido alkylidene N-heterocyclic carbene (NHC) complexes (W01 - W09) of the general formula [W(S)(CHCMe3)(X)(NHC)(CMe3CN)+B(ArF)4-] (NHC = 1,3-dimesitylimidazol-2-ylidene, IMes; 1,3-dimesityl-4,5-dichloroimidazol-2-ylidene, IMesCl2; 1,3-bis(2,6-xdiisopropyl)phenyl)imidazol-2-ylidene, IDipp; X = Cl, C6F5O, 2,6-Ph2-C6H3; B(ArF)4- = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) are used as initiators in the stereoselective ring-opening metathesis polymerization (ROMP) of (+) 2,3-endo, exo-dicarbomethoxynorborn-5-ene ((+)DCMNBE, M1). Trans-isospecifity up to 84% is achieved along with varying percentages of cis-syndiospecifity. The different extent of trans-isospecifity is compared to the one of related benchmark cationic molybdenum and tungsten imido and tungsten oxo alkylidene NHC complexes. Mechanistic investigations suggest that the syn-isomer of a nitrile-free initiator reacts with M1 presumably in an eneanti fashion to yield a syn-first insertion product via turnstile rearrangement, which accounts for the predominant trans-isospecifity of the polymerization. The cis-syndiotactic sequences are proposed to stem from the competing enesyn addition of M1 to a nitrile-containing syn-isomer of the initiator. | en |
dc.description.sponsorship | Deutsche Forschungsgemeinschaft | de |
dc.description.sponsorship | Projekt DEAL | de |
dc.language.iso | en | de |
dc.relation.uri | doi:10.1002/macp.202200350 | de |
dc.rights | info:eu-repo/semantics/openAccess | de |
dc.rights.uri | https://creativecommons.org/licenses/by/4.0/ | de |
dc.subject.ddc | 540 | de |
dc.title | Stereoselective ring‐opening metathesis polymerization with tungsten sulfido alkylidene N‐heterocyclic carbene complexes | en |
dc.type | article | de |
dc.date.updated | 2023-04-19T20:28:23Z | - |
ubs.fakultaet | Chemie | de |
ubs.institut | Institut für Polymerchemie | de |
ubs.publikation.seiten | 6 | de |
ubs.publikation.source | Macromolecular chemistry and physics 224 (2022), No. 2200350 | de |
ubs.publikation.typ | Zeitschriftenartikel | de |
Enthalten in den Sammlungen: | 03 Fakultät Chemie |
Dateien zu dieser Ressource:
Datei | Beschreibung | Größe | Format | |
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MACP_MACP202200350.pdf | 608,86 kB | Adobe PDF | Öffnen/Anzeigen |
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