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Tungsten Sulfido Alkylidene and Cationic Tungsten Sulfido Alkylidene N-Heterocyclic Carbene Complexes

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    Tungsten Sulfido Alkylidene and Cationic Tungsten Sulfido Alkylidene N-Heterocyclic Carbene Complexes
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    • Philipp M. Hauser
      Philipp M. Hauser
      Institute of Polymer Chemistry, University of Stuttgart, Pfaffenwaldring 55, D-70569Stuttgart, Germany
      More by Philipp M. Hauser
    • Katrin Gugeler
      Katrin Gugeler
      Institute of Theoretical Chemistry, University of Stuttgart, Pfaffenwaldring 55, D-70569Stuttgart, Germany
      More by Katrin Gugeler
    • Wolfgang Frey
      Wolfgang Frey
      Institute of Organic Chemistry, University of Stuttgart, Pfaffenwaldring 55, D-70569Stuttgart, Germany
      More by Wolfgang Frey
    • Johannes Kästner
      Johannes Kästner
      Institute of Theoretical Chemistry, University of Stuttgart, Pfaffenwaldring 55, D-70569Stuttgart, Germany
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      Orcidhttps://orcid.org/0000-0001-6178-7669
    • Michael R. Buchmeiser*
      Michael R. Buchmeiser
      Institute of Polymer Chemistry, University of Stuttgart, Pfaffenwaldring 55, D-70569Stuttgart, Germany
      German Institutes of Textile and Fiber Research, Körschtalstrasse 26, D-73770Denkendorf, Germany
      *Email: [email protected]
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      Orcidhttps://orcid.org/0000-0001-6472-5156
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    Organometallics

    Cite this: Organometallics 2021, 40, 23, 4026–4034
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    https://doi.org/10.1021/acs.organomet.1c00577
    Published November 17, 2021
    Copyright © 2021 The Authors. Published by American Chemical Society
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    Abstract

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    High-oxidation-state group 6 metal alkylidenes have been dominated by imido and oxo ligands. Here, the first neutral tungsten sulfido alkylidene and cationic tungsten sulfido alkylidene N-heterocyclic carbene (NHC) complexes are presented. A synthesis route that entails the reaction of the corresponding tungsten alkylidyne precursors with H2S in tetrahydrofuran is outlined. Schrock-type complexes bearing chlorides as well as pentafluorophenoxide ligands were synthesized, while variations in the NHC (1,3-dimesityl-1,3-dihydro-2H-imidazol-2-ylidene (IMes), 1,3-dimesityl-4,5-dichloro-1,3-dihydro-2H-imidazol-2-ylidene (IMesCl2), and 1,3-bis(2,6-diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene (IDipp)) as well as in the anionic ligand (chloride, pentafluorophenoxide, and 2,6-diphenylphenoxide) were carried out for the cationic tungsten sulfido alkylidene NHC complexes. All complexes were tested in benchmark olefin metathesis reactions in which the cationic tungsten sulfido alkylidene NHC complexes showed high productivities. Atomic charges were calculated for several cationic tungsten sulfido alkylidene NHC complexes and compared to those of the analogous tungsten oxo and imido complexes. These calculations revealed charge distribution between the NHC and the metal, yet lower charges at the metal and less polarization of the metal alkylidene bond compared to their tungsten oxo and imido analogs.

    Copyright © 2021 The Authors. Published by American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.organomet.1c00577.

    • Experimental details, NMR spectra of the compounds mentioned in the paper and crystal data as well as optimized geometries, NMR spectra, further information on metathesis reactions and theoretical calculations (PDF)

    • Cartesian coordinates for crystal structures and optimized geometries (XYZ)

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    CCDC 2113822–2113828 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    This article is cited by 5 publications.

    1. Koushani Kundu, Severin Haid, Moritz R. Schäfer, Wolfgang Frey, Johannes Kästner, Michael R. Buchmeiser. Origin of Stereoselectivity in Ring Opening Metathesis Polymerization with Cationic Molybdenum Imido Alkylidene CAAC Complexes. ACS Catalysis 2025, 15 (2) , 738-747. https://doi.org/10.1021/acscatal.4c07610
    2. Vineet K. Jakhar, Yu-Hsuan Shen, Rinku Yadav, Soufiane S. Nadif, Ion Ghiviriga, Khalil A. Abboud, Daniel W. Lester, Adam S. Veige. Tethered Alkylidenes for REMP from Carbon Disulfide Cleavage. Inorganic Chemistry 2024, 63 (26) , 12207-12217. https://doi.org/10.1021/acs.inorgchem.4c01522
    3. Alejandro Bugarin, Siddappa A. Patil, Ryan Q. Tran, Kostiantyn O. Marichev. Metal complexes of backbone-halogenated imidazol-2-ylidenes. Inorganica Chimica Acta 2024, 572 , 122263. https://doi.org/10.1016/j.ica.2024.122263
    4. Koushani Kundu, Janis V. Musso, Mathis J. Benedikter, Wolfgang Frey, Katrin Gugeler, Johannes Kästner, Michael R. Buchmeiser. Neutral and Cationic Molybdenum Imido Alkylidene Cyclic Alkyl Amino Carbene (CAAC) Complexes for Olefin Metathesis. Chemistry – A European Journal 2023, 29 (52) https://doi.org/10.1002/chem.202301818
    5. Michael R. Buchmeiser, Patrick Probst, Dongren Wang, Philipp Hauser. Stereoselective Ring‐Opening Metathesis Polymerization with Tungsten Sulfido Alkylidene N ‐Heterocyclic Carbene Complexes. Macromolecular Chemistry and Physics 2023, 224 (3) https://doi.org/10.1002/macp.202200350
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    Organometallics

    Cite this: Organometallics 2021, 40, 23, 4026–4034
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.organomet.1c00577
    Published November 17, 2021
    Copyright © 2021 The Authors. Published by American Chemical Society
    Request reuse permissions

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