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δ and φ back-donation in An(IV) metallacycles

In all known examples of metal–ligand (M–L) δ and φ bonds, the metal orbitals are aligned to the ligand orbitals in a “head-to-head” or “side-to-head” fashion. Here, we report two fundamentally new types of M–L δ and φ interactions; “head-to-side” δ and “side-to-side” φ back-bonding, found in comple...

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Autores principales: Kelley, Morgan P., Popov, Ivan A., Jung, Julie, Batista, Enrique R., Yang, Ping
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7096508/
https://www.ncbi.nlm.nih.gov/pubmed/32214090
http://dx.doi.org/10.1038/s41467-020-15197-w
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author Kelley, Morgan P.
Popov, Ivan A.
Jung, Julie
Batista, Enrique R.
Yang, Ping
author_facet Kelley, Morgan P.
Popov, Ivan A.
Jung, Julie
Batista, Enrique R.
Yang, Ping
author_sort Kelley, Morgan P.
collection PubMed
description In all known examples of metal–ligand (M–L) δ and φ bonds, the metal orbitals are aligned to the ligand orbitals in a “head-to-head” or “side-to-head” fashion. Here, we report two fundamentally new types of M–L δ and φ interactions; “head-to-side” δ and “side-to-side” φ back-bonding, found in complexes of metallacyclopropenes and metallacyclocumulenes of actinides (Pa–Pu) that makes them distinct from their corresponding Group 4 analogues. In addition to the known Th and U complexes, our calculations include complexes of Pa, Np, and Pu. In contrast with conventional An–C bond decreasing, due to the actinide contraction, the An–C distance increases from Pa to Pu. We demonstrate that the direct L–An σ and π donations combined with the An–L δ or φ back-donations are crucial in explaining this non-classical trend of the An–L bond lengths in both series, underscoring the significance of these δ/φ back-donation interactions, and their importance for complexes of Pa and U in particular.
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spelling pubmed-70965082020-03-27 δ and φ back-donation in An(IV) metallacycles Kelley, Morgan P. Popov, Ivan A. Jung, Julie Batista, Enrique R. Yang, Ping Nat Commun Article In all known examples of metal–ligand (M–L) δ and φ bonds, the metal orbitals are aligned to the ligand orbitals in a “head-to-head” or “side-to-head” fashion. Here, we report two fundamentally new types of M–L δ and φ interactions; “head-to-side” δ and “side-to-side” φ back-bonding, found in complexes of metallacyclopropenes and metallacyclocumulenes of actinides (Pa–Pu) that makes them distinct from their corresponding Group 4 analogues. In addition to the known Th and U complexes, our calculations include complexes of Pa, Np, and Pu. In contrast with conventional An–C bond decreasing, due to the actinide contraction, the An–C distance increases from Pa to Pu. We demonstrate that the direct L–An σ and π donations combined with the An–L δ or φ back-donations are crucial in explaining this non-classical trend of the An–L bond lengths in both series, underscoring the significance of these δ/φ back-donation interactions, and their importance for complexes of Pa and U in particular. Nature Publishing Group UK 2020-03-25 /pmc/articles/PMC7096508/ /pubmed/32214090 http://dx.doi.org/10.1038/s41467-020-15197-w Text en © This is a U.S. government work and not under copyright protection in the U.S.; foreign copyright protection may apply 2020 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/.
spellingShingle Article
Kelley, Morgan P.
Popov, Ivan A.
Jung, Julie
Batista, Enrique R.
Yang, Ping
δ and φ back-donation in An(IV) metallacycles
title δ and φ back-donation in An(IV) metallacycles
title_full δ and φ back-donation in An(IV) metallacycles
title_fullStr δ and φ back-donation in An(IV) metallacycles
title_full_unstemmed δ and φ back-donation in An(IV) metallacycles
title_short δ and φ back-donation in An(IV) metallacycles
title_sort δ and φ back-donation in an(iv) metallacycles
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7096508/
https://www.ncbi.nlm.nih.gov/pubmed/32214090
http://dx.doi.org/10.1038/s41467-020-15197-w
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