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Autor(en): Kundu, Koushani
Musso, Janis V.
Benedikter, Mathis J.
Frey, Wolfgang
Gugeler, Katrin
Kästner, Johannes
Buchmeiser, Michael R.
Titel: Neutral and cationic molybdenum imido alkylidene cyclic alkyl amino carbene (CAAC) complexes for olefin metathesis
Erscheinungsdatum: 2023
Dokumentart: Zeitschriftenartikel
Seiten: 10
Erschienen in: Chemistry - a European journal 29 (2023), No. e202301818
URI: http://nbn-resolving.de/urn:nbn:de:bsz:93-opus-ds-137529
http://elib.uni-stuttgart.de/handle/11682/13752
http://dx.doi.org/10.18419/opus-13733
ISSN: 0947-6539
1521-3765
Zusammenfassung: The first neutral and cationic Mo imido alkylidene cyclic alkyl amino carbene (CAAC) complexes of the general formulae [Mo(N-Ar)(CHCMe2Ph)(X)2(CAAC)] and [Mo(N−Ar)(CHCMe2Ph)(X)(CAAC)][B(ArF)4] (X=Br, Cl, OTf, OC6F5; CAAC=1-(2,6-iPr2-C6H3)-3,3,5,5-tetramethyltetrahydropyrrol-2-ylidene) have been synthesized from molybdenum imido bishalide alkylidene DME precursors. Different combinations of the imido and “X” ligands have been employed to understand synthetic peculiarities. Selected complexes have been characterized by single-crystal X-ray analysis. Due to the pronounced σ-donor/π-acceptor characteristics of CAACs, the corresponding neutral and cationic molybdenum imido alkylidene CAAC complexes do not require the presence of stabilizing donor ligands such as nitriles. Calculations on the PBE0-D3BJ/def2-TZVP level for PBE0-D3BJ/def2-SVP optimized geometries revealed partial charges at molybdenum similar to the corresponding molybdenum imido alkylidene N-heterocyclic carbene (NHC) complexes with a slightly higher polarization of the molybdenum alkylidene bond in the CAAC complexes. All cationic complexes have been tested in olefin metathesis reactions and showed improved activity compared to the analogous NHC complexes for hydrocarbon-based substrates, allowing for turnover numbers (TONs) up to 9500 even at room temperature. Some Mo imido alkylidene CAAC complexes are tolerant towards functional groups like thioethers and sulfonamides.
Enthalten in den Sammlungen:03 Fakultät Chemie

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