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Accessing the main-group metal formyl scaffold through CO-activation in beryllium hydride complexes

Carbon monoxide (CO) is an indispensable C1 building block. For decades this abundant gas has been employed in hydroformylation and Pausen-Khand catalysis, amongst many related chemistries, where a single, non-coupled CO fragment is delivered to an organic molecule. Despite this, organometallic spec...

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Autores principales: Hadlington, Terrance J., Szilvási, Tibor
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8786820/
https://www.ncbi.nlm.nih.gov/pubmed/35075124
http://dx.doi.org/10.1038/s41467-022-28095-0
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author Hadlington, Terrance J.
Szilvási, Tibor
author_facet Hadlington, Terrance J.
Szilvási, Tibor
author_sort Hadlington, Terrance J.
collection PubMed
description Carbon monoxide (CO) is an indispensable C1 building block. For decades this abundant gas has been employed in hydroformylation and Pausen-Khand catalysis, amongst many related chemistries, where a single, non-coupled CO fragment is delivered to an organic molecule. Despite this, organometallic species which react with CO to yield C1 products remain rare, and are elusive for main group metal complexes. Here, we describe a range of amido-beryllium hydride complexes, and demonstrate their reactivity towards CO, in its mono-insertion into the Be-H bonds of these species. The small radius of the Be(2+) ion in conjunction with the non-innocent pendant phosphine moiety of the developed ligands leads to a unique beryllium formyl complex with an ylidic P-(CO)C fragment, whereby the carbon centre, remarkably, datively binds Be. This, alongside reactivity toward carbon dioxide, sheds light on the insertion chemistry of the Be-H bond, complimenting the long-known chemistry of the heavier Alkaline Earth hydrides.
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spelling pubmed-87868202022-02-07 Accessing the main-group metal formyl scaffold through CO-activation in beryllium hydride complexes Hadlington, Terrance J. Szilvási, Tibor Nat Commun Article Carbon monoxide (CO) is an indispensable C1 building block. For decades this abundant gas has been employed in hydroformylation and Pausen-Khand catalysis, amongst many related chemistries, where a single, non-coupled CO fragment is delivered to an organic molecule. Despite this, organometallic species which react with CO to yield C1 products remain rare, and are elusive for main group metal complexes. Here, we describe a range of amido-beryllium hydride complexes, and demonstrate their reactivity towards CO, in its mono-insertion into the Be-H bonds of these species. The small radius of the Be(2+) ion in conjunction with the non-innocent pendant phosphine moiety of the developed ligands leads to a unique beryllium formyl complex with an ylidic P-(CO)C fragment, whereby the carbon centre, remarkably, datively binds Be. This, alongside reactivity toward carbon dioxide, sheds light on the insertion chemistry of the Be-H bond, complimenting the long-known chemistry of the heavier Alkaline Earth hydrides. Nature Publishing Group UK 2022-01-24 /pmc/articles/PMC8786820/ /pubmed/35075124 http://dx.doi.org/10.1038/s41467-022-28095-0 Text en © The Author(s) 2022 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Hadlington, Terrance J.
Szilvási, Tibor
Accessing the main-group metal formyl scaffold through CO-activation in beryllium hydride complexes
title Accessing the main-group metal formyl scaffold through CO-activation in beryllium hydride complexes
title_full Accessing the main-group metal formyl scaffold through CO-activation in beryllium hydride complexes
title_fullStr Accessing the main-group metal formyl scaffold through CO-activation in beryllium hydride complexes
title_full_unstemmed Accessing the main-group metal formyl scaffold through CO-activation in beryllium hydride complexes
title_short Accessing the main-group metal formyl scaffold through CO-activation in beryllium hydride complexes
title_sort accessing the main-group metal formyl scaffold through co-activation in beryllium hydride complexes
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8786820/
https://www.ncbi.nlm.nih.gov/pubmed/35075124
http://dx.doi.org/10.1038/s41467-022-28095-0
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