Nature Communications (May 2023)

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

  • Marcel Härterich,
  • Alexander Matler,
  • Rian D. Dewhurst,
  • Andreas Sachs,
  • Kai Oppel,
  • Andreas Stoy,
  • Holger Braunschweig

DOI
https://doi.org/10.1038/s41467-023-36251-3
Journal volume & issue
Vol. 14, no. 1
pp. 1 – 7

Abstract

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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.