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Molybdenum and Tungsten Alkylidyne Complexes Containing Mono-, Bi-, and Tridentate N-Heterocyclic Carbenes

  • Iris Elser
    Iris Elser
    Institute of Polymer Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
    More by Iris Elser
  • Jonas Groos
    Jonas Groos
    Institute of Polymer Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
    More by Jonas Groos
  • Philipp M. Hauser
    Philipp M. Hauser
    Institute of Polymer Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
  • Maximilian Koy
    Maximilian Koy
    Institute of Polymer Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
  • Melita van der Ende
    Melita van der Ende
    Institute of Polymer Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
  • Dongren Wang
    Dongren Wang
    Institute of Polymer Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
    More by Dongren Wang
  • Wolfgang Frey
    Wolfgang Frey
    Institute of Organic Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
  • Klaus Wurst
    Klaus Wurst
    Institute of General, Inorganic and Theoretical Chemistry, University of Innsbruck, A-6020 Innsbruck, Austria
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  • Jan Meisner
    Jan Meisner
    Institute for Theoretical Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
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  • Felix Ziegler
    Felix Ziegler
    Institute of Polymer Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
  • Johannes Kästner
    Johannes Kästner
    Institute for Theoretical Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
  • , and 
  • Michael R. Buchmeiser*
    Michael R. Buchmeiser
    Institute of Polymer Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
    *(M.R.B.): [email protected]
Cite this: Organometallics 2019, 38, 21, 4133–4146
Publication Date (Web):October 18, 2019
https://doi.org/10.1021/acs.organomet.9b00481
Copyright © 2019 American Chemical Society

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    Abstract

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    New tungsten and molybdenum alkylidyne complexes bearing mono-, bi-, and tridentate N-heterocyclic carbenes (NHCs) have been synthesized. Formation of unprecedented structures in complexes bearing N-tert-butyl substituents on the imidazol(in)-2-ylidene was observed, leading to molybdenum complexes containing an abnormal carbene (Mo-4) and a bridging O,C,C-pincer ligand (Mo-10) and to a tungsten complex containing a cationic imidazolinium-tagged alkoxide forming an inner salt with an anionic tungsten center (W-5). Both the abnormal carbene binding in Mo-4 and the O,C,C-pincer-type structure of Mo-10 were confirmed by single-crystal X-ray analysis, and the proposed structure of W-5 is supported by the single-crystal X-ray structure of a minor byproduct (W-8) formed during the synthesis of W-4, displaying the aforementioned inner-salt-like structure. The novel alkylidyne complexes were also investigated for their capability to form a previously postulated quasi-cationic species with a weakly coordinating anion (WCA) during the alkyne homometathesis of 1-phenyl-1-propyne. Overall, incorporation of bidentate and strongly σ donating NHCs as well as introduction of better leaving groups did not lead to the expected increase in catalytic activity. Despite identical ligand spheres, changing from molybdenum to tungsten led to complete loss of activity in the bidentate systems.

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.organomet.9b00481.

    • Spectra of all novel compounds/mechanistic experiments/in situ NMR measurements of reaction mixtures, single-crystal X-ray data of Mo-3, Mo-4, Mo-5, Mo-8, Mo-10, W-4, and W-8, literature for the synthesis of known compounds, and information on calculation of the TEP (PDF)

    • Cartesian coordinates of the calculated structures (XYZ)

    Accession Codes

    CCDC 15313911531393, 18613211861324, and 1897061 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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    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

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