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A step-for-step main-group replica of the Fischer carbene synthesis at a borylene carbonyl

Author

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  • Marcel Härterich

    (Julius-Maximilians-Universität Würzburg, Am Hubland
    Julius-Maximilians-Universität Würzburg, Am Hubland)

  • Alexander Matler

    (Julius-Maximilians-Universität Würzburg, Am Hubland
    Julius-Maximilians-Universität Würzburg, Am Hubland)

  • Rian D. Dewhurst

    (Julius-Maximilians-Universität Würzburg, Am Hubland
    Julius-Maximilians-Universität Würzburg, Am Hubland)

  • Andreas Sachs

    (Julius-Maximilians-Universität Würzburg, Am Hubland
    Julius-Maximilians-Universität Würzburg, Am Hubland)

  • Kai Oppel

    (Julius-Maximilians-Universität Würzburg, Am Hubland
    Julius-Maximilians-Universität Würzburg, Am Hubland)

  • Andreas Stoy

    (Julius-Maximilians-Universität Würzburg, Am Hubland
    Julius-Maximilians-Universität Würzburg, Am Hubland)

  • Holger Braunschweig

    (Julius-Maximilians-Universität Würzburg, Am Hubland
    Julius-Maximilians-Universität Würzburg, Am Hubland)

Abstract

The Fischer carbene synthesis, involving the conversion of a transition metal (TM)-bound CO ligand to a carbene ligand of the form [=C(OR’)R] (R, R’ = organyl groups), is one of the seminal reactions in the history of organometallic chemistry. Carbonyl complexes of p-block elements, of the form [E(CO)n] (E = main-group fragment), are much less abundant than their TM cousins; this scarcity and the general instability of low-valent p-block species means that replicating the historical reactions of TM carbonyls is often very difficult. Here we present a step-for-step replica of the Fischer carbene synthesis at a borylene carbonyl involving nucleophilic attack at the carbonyl carbon followed by electrophilic quenching at the resultant acylate oxygen atom. These reactions provide borylene acylates and alkoxy-/silyloxy-substituted alkylideneboranes, main-group analogues of the archetypal transition metal acylate and Fischer carbene families, respectively. When either the incoming electrophile or the boron center has a modest steric profile, the electrophile instead attacks at the boron atom, leading to carbene-stabilized acylboranes – boron analogues of the well-known transition metal acyl complexes. These results constitute faithful main-group replicas of a number of historical organometallic processes and pave the way to further advances in the field of main-group metallomimetics.

Suggested Citation

  • Marcel Härterich & Alexander Matler & Rian D. Dewhurst & Andreas Sachs & Kai Oppel & Andreas Stoy & Holger Braunschweig, 2023. "A step-for-step main-group replica of the Fischer carbene synthesis at a borylene carbonyl," Nature Communications, Nature, vol. 14(1), pages 1-7, December.
  • Handle: RePEc:nat:natcom:v:14:y:2023:i:1:d:10.1038_s41467-023-36251-3
    DOI: 10.1038/s41467-023-36251-3
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    References listed on IDEAS

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    1. Holger Braunschweig & Rian D. Dewhurst & Florian Hupp & Marco Nutz & Krzysztof Radacki & Christopher W. Tate & Alfredo Vargas & Qing Ye, 2015. "Multiple complexation of CO and related ligands to a main-group element," Nature, Nature, vol. 522(7556), pages 327-330, June.
    2. Philip P. Power, 2010. "Main-group elements as transition metals," Nature, Nature, vol. 463(7278), pages 171-177, January.
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