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N-Heterocyclic Carbene-Stabilized Germanium and Tin Analogues of Heavier Nitriles: Synthesis, Reactivity, and Catalytic Application

  • Vitaly Nesterov
    Vitaly Nesterov
    Department of Chemistry, WACKER-Institute of Silicon Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstraße 4, 85748 Garching bei München, Germany
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  • , 
  • Ramona Baierl
    Ramona Baierl
    Department of Chemistry, WACKER-Institute of Silicon Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstraße 4, 85748 Garching bei München, Germany
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  • , 
  • Franziska Hanusch
    Franziska Hanusch
    Department of Chemistry, WACKER-Institute of Silicon Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstraße 4, 85748 Garching bei München, Germany
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    Orcidhttp://orcid.org/0000-0002-9509-194X
  • , 
  • Arturo Espinosa Ferao
    Arturo Espinosa Ferao
    Departamento de Química Orgánica, Facultad de Química, Universidad de Murcia, Campus de Espinardo, 30100 Murcia, Spain
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    Orcidhttp://orcid.org/0000-0003-4452-0430
  • , and 
  • Shigeyoshi Inoue*
    Shigeyoshi Inoue
    Department of Chemistry, WACKER-Institute of Silicon Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstraße 4, 85748 Garching bei München, Germany
    *[email protected]
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    Orcidhttp://orcid.org/0000-0001-6685-6352
Cite this: J. Am. Chem. Soc. 2019, 141, 37, 14576–14580
Publication Date (Web):September 2, 2019
https://doi.org/10.1021/jacs.9b08741
Copyright © 2019 American Chemical Society
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    Abstract

    Abstract Image

    The synthesis of stable heavier analogues of nitriles as monomeric tetrylene–phosphinidenes MesTerEP(IDipp) (E = Ge, Sn; MesTer = 2,6-Mes2C6H3, IDipp = C([N-(2,6-iPr2C6H4)CH]2) was achieved by taking advantage of NHC (N-heterocyclic carbene, here IDipp) coordination to the low-valent phosphorus center. Multiple bonding character of the E–P bonds was examined experimentally and computationally. Both germanium and tin compounds undergo [2+2] cycloaddition with diphenylketene, whereas reaction of the tin derivative with tris(pentafluorophenyl)borane provided unique “push–pull” phosphastannene (MesTer)(Ar)Sn = P(IDipp) (Ar = C6F4[B(F)(C6F5)2]). Going further, we demonstrated the potential of tetrylene–phosphinidene complexes in catalytic hydroboration of carbonyl compounds.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.9b08741.

    • Full synthetic and characterizing data for new compounds, representative NMR spectra, details of computational studies (PDF)

    • Crystallographic data (CCDC Compound 1: 1946724, Compound 2: 1946725, Compound 3: 1946726, Compound 4: 1946727, Compound 5: 1946728) (CIF)

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