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dc.contributor.authorHollfelder, Christoph O.
dc.contributor.authorMeermann-Zimmermann, Melanie
dc.contributor.authorSpiridopoulos, Georgios
dc.contributor.authorWerner, Daniel
dc.contributor.authorTörnroos, Karl Wilhelm
dc.contributor.authorMaichle-Mössmer, Cäcilia
dc.contributor.authorAnwander, Reiner
dc.date.accessioned2020-03-18T12:57:22Z
dc.date.available2020-03-18T12:57:22Z
dc.date.issued2019
dc.PublishedHollfelder, Meermann-Zimmermann, Spiridopoulos, Werner, Törnroos, Maichle-Mössmer, Anwander. C–H-Bond Activation and Isoprene Polymerization Studies Applying Pentamethylcyclopentadienyl-Supported Rare-Earth-Metal Bis(Tetramethylaluminate) and Dimethyl Complexes. Molecules. 2019;24(20):3703eng
dc.identifier.issn1420-3049en_US
dc.identifier.urihttps://hdl.handle.net/1956/21528
dc.description.abstractAs previously shown for lutetium and yttrium, 1,2,3,4,5-pentamethylcyclopentadienyl (C5Me5 = Cp*)-bearing rare-earth metal dimethyl half-sandwich complexes [Cp*LnMe2]3 are now also accessible for holmium, dysprosium, and terbium via tetramethylaluminato cleavage of [Cp*Ln(AlMe4)2] with diethyl ether (Ho, Dy) and tert-butyl methyl ether (TBME) (Tb). C–H-bond activation and ligand redistribution reactions are observed in case of terbium and are dominant for the next larger-sized gadolinium, as evidenced by the formation of mixed methyl/methylidene clusters [(Cp*Ln)5(CH2)(Me)8] and metallocene dimers [Cp*2Ln(AlMe4)]2 (Ln = Tb, Gd). Applying TBME as a “cleaving” reagent can result in both TBME deprotonation and ether cleavage, as shown for the formation of the 24-membered macrocycle [(Cp*Gd)2(Me)(CH2OtBu)2(AlMe4)]4 or monolanthanum complex [Cp*La(AlMe4){Me3Al(CH2)OtBu}] and monoyttrium complex [Cp*Y(AlMe4)(Me3AlOtBu)], respectively. Complexes [Cp*Ln(AlMe4)2] (Ln = Ho, Dy, Tb, Gd) and [Cp*LnMe2]3 (Ln = Ho, Dy) are applied in isoprene and 1,3-butadiene polymerization, upon activation with borates [Ph3C][B(C6F5)4] and [PhNHMe2][B(C6F5)4], as well as borane B(C6F5)3. The trans-directing effect of AlMe3 in the binary systems [Cp*Ln(AlMe4)2]/borate is revealed and further corroborated by the fabrication of high-cis-1,4 polybutadiene (97%) with “aluminum-free” [Cp*DyMe2]3/[Ph3C][B(C6F5)4]. The formation of multimetallic active species is supported by the polymerization activity of pre-isolated cluster [(Cp*Ho)3Me4(CH2)(thf)2].en_US
dc.language.isoengeng
dc.publisherMDPIen_US
dc.rightsAttribution CC BYeng
dc.rights.urihttp://creativecommons.org/licenses/by/4.0eng
dc.titleC–H-Bond Activation and Isoprene Polymerization Studies Applying Pentamethylcyclopentadienyl-Supported Rare-Earth-Metal Bis(Tetramethylaluminate) and Dimethyl Complexesen_US
dc.typePeer reviewed
dc.typeJournal article
dc.date.updated2020-01-02T09:24:09Z
dc.description.versionpublishedVersionen_US
dc.rights.holderCopyright 2019 The Author(s)en_US
dc.identifier.doihttps://doi.org/10.3390/molecules24203703
dc.identifier.cristin1764959
dc.source.journalMolecules


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