A step-for-step main-group replica of the Fischer carbene synthesis at a borylene carbonyl
Please always quote using this URN: urn:nbn:de:bvb:20-opus-357270
- 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 weThe 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.…
Author: | Marcel Härterich, Alexander Matler, Rian D. Dewhurst, Andreas Sachs, Kai Oppel, Andreas Stoy, Holger Braunschweig |
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URN: | urn:nbn:de:bvb:20-opus-357270 |
Document Type: | Journal article |
Faculties: | Fakultät für Chemie und Pharmazie / Institut für Anorganische Chemie |
Language: | English |
Parent Title (English): | Nature Communications |
Year of Completion: | 2023 |
Volume: | 14 |
Article Number: | 2764 |
Source: | Nature Communications (2023) 14:2764. https://doi.org/10.1038/s41467-023-36251-3 |
DOI: | https://doi.org/10.1038/s41467-023-36251-3 |
Dewey Decimal Classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 546 Anorganische Chemie |
Tag: | chemical bonding; ligands |
Release Date: | 2024/04/30 |
Licence (German): | CC BY: Creative-Commons-Lizenz: Namensnennung 4.0 International |