A step-for-step main-group replica of the Fischer carbene synthesis at a borylene carbonyl
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...
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Nature Portfolio
2023-05-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-36251-3 |
| _version_ | 1797827473256218624 |
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| author | Marcel Härterich Alexander Matler Rian D. Dewhurst Andreas Sachs Kai Oppel Andreas Stoy Holger Braunschweig |
| author_facet | Marcel Härterich Alexander Matler Rian D. Dewhurst Andreas Sachs Kai Oppel Andreas Stoy Holger Braunschweig |
| author_sort | Marcel Härterich |
| collection | DOAJ |
| description | 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. |
| first_indexed | 2024-04-09T12:48:52Z |
| format | Article |
| id | doaj.art-dbab5c0d08d0411180aed3b43ba0cd1d |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-04-09T12:48:52Z |
| publishDate | 2023-05-01 |
| publisher | Nature Portfolio |
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| series | Nature Communications |
| spelling | doaj.art-dbab5c0d08d0411180aed3b43ba0cd1d2023-05-14T11:22:01ZengNature PortfolioNature Communications2041-17232023-05-011411710.1038/s41467-023-36251-3A step-for-step main-group replica of the Fischer carbene synthesis at a borylene carbonylMarcel Härterich0Alexander Matler1Rian D. Dewhurst2Andreas Sachs3Kai Oppel4Andreas Stoy5Holger Braunschweig6Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am HublandInstitute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am HublandInstitute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am HublandInstitute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am HublandInstitute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am HublandInstitute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am HublandInstitute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am HublandAbstract 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.https://doi.org/10.1038/s41467-023-36251-3 |
| spellingShingle | Marcel Härterich Alexander Matler Rian D. Dewhurst Andreas Sachs Kai Oppel Andreas Stoy Holger Braunschweig A step-for-step main-group replica of the Fischer carbene synthesis at a borylene carbonyl Nature Communications |
| title | A step-for-step main-group replica of the Fischer carbene synthesis at a borylene carbonyl |
| title_full | A step-for-step main-group replica of the Fischer carbene synthesis at a borylene carbonyl |
| title_fullStr | A step-for-step main-group replica of the Fischer carbene synthesis at a borylene carbonyl |
| title_full_unstemmed | A step-for-step main-group replica of the Fischer carbene synthesis at a borylene carbonyl |
| title_short | A step-for-step main-group replica of the Fischer carbene synthesis at a borylene carbonyl |
| title_sort | step for step main group replica of the fischer carbene synthesis at a borylene carbonyl |
| url | https://doi.org/10.1038/s41467-023-36251-3 |
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