Torsion Effects Beyond the δ Bond and the Role of π Metal-Ligand Interactions
Previous studies on bimetallic paddlewheel compounds have established a direct correlation between metal–metal distance and ligand torsion angles, leading to the rule that higher torsion results in longer metal-metal bond distances. Here, the new discovery based on diarylformamidinate Ru₂⁵⁺ paddlewh...
| Autores: | , , , , , , , |
|---|---|
| Tipo de recurso: | artículo |
| Fecha de publicación: | 2024 |
| País: | España |
| Institución: | Universidad Complutense de Madrid (UCM) |
| Repositorio: | Docta Complutense |
| Idioma: | inglés |
| OAI Identifier: | oai:docta.ucm.es:20.500.14352/113725 |
| Acceso en línea: | https://hdl.handle.net/20.500.14352/113725 |
| Access Level: | acceso abierto |
| Palabra clave: | 546 Bidentate ligands Diruthenium Metal–metal bond Paddlewheel Electronic structure Ciencias 23 Química |
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Torsion Effects Beyond the δ Bond and the Role of π Metal-Ligand InteractionsInchausti Vallés, AlmudenaMollfulleda, RosaSwart, MarcelPerles Hernáez, JosefinaHerrero Domínguez, SantiagoGarcía Baonza, ValentínTaravillo Corralo, MercedesLobato Fernández, Álvaro546Bidentate ligandsDirutheniumMetal–metal bondPaddlewheelElectronic structureCiencias23 QuímicaPrevious studies on bimetallic paddlewheel compounds have established a direct correlation between metal–metal distance and ligand torsion angles, leading to the rule that higher torsion results in longer metal-metal bond distances. Here, the new discovery based on diarylformamidinate Ru₂⁵⁺ paddlewheel compounds [Ru2Cl(DArF)4] that show an opposite behavior is reported: higher torsions lead to shorter metal–metal distances. This discovery challenges the assumption that internal rotation solely impacts the δ bond. By combining experimental and theoretical techniques, it is demostrated that this trend is associated with previously overlooked π metal-ligand interactions. These π metal-ligand interactions are a direct consequence of the paddlewheel structure and the conjugated nature of the bidentate ligands. This findings offer far-reaching insights into the influence of equatorial ligands and their π-conjugation characteristics on the electronic properties of paddlewheel complexes. That this effect is not exclusive of diruthenium compounds but also occurs in other bimetallic cores such as ditungsten or dirhodium is demonstrated, and with other ligands showing allyl type conjugation. These results provide a novel approach for fine-tuning the properties of these compounds with significant implications for materials design.WileyUniversidad Complutense de Madrid20242024-07-0320242024-07-03journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/20.500.14352/113725reponame:Docta Complutenseinstname:Universidad Complutense de Madrid (UCM)Inglésengopen accesshttp://purl.org/coar/access_right/c_abf2Attribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:docta.ucm.es:20.500.14352/1137252026-06-02T12:44:21Z |
| dc.title.none.fl_str_mv |
Torsion Effects Beyond the δ Bond and the Role of π Metal-Ligand Interactions |
| title |
Torsion Effects Beyond the δ Bond and the Role of π Metal-Ligand Interactions |
| spellingShingle |
Torsion Effects Beyond the δ Bond and the Role of π Metal-Ligand Interactions Inchausti Vallés, Almudena 546 Bidentate ligands Diruthenium Metal–metal bond Paddlewheel Electronic structure Ciencias 23 Química |
| title_short |
Torsion Effects Beyond the δ Bond and the Role of π Metal-Ligand Interactions |
| title_full |
Torsion Effects Beyond the δ Bond and the Role of π Metal-Ligand Interactions |
| title_fullStr |
Torsion Effects Beyond the δ Bond and the Role of π Metal-Ligand Interactions |
| title_full_unstemmed |
Torsion Effects Beyond the δ Bond and the Role of π Metal-Ligand Interactions |
| title_sort |
Torsion Effects Beyond the δ Bond and the Role of π Metal-Ligand Interactions |
| dc.creator.none.fl_str_mv |
Inchausti Vallés, Almudena Mollfulleda, Rosa Swart, Marcel Perles Hernáez, Josefina Herrero Domínguez, Santiago García Baonza, Valentín Taravillo Corralo, Mercedes Lobato Fernández, Álvaro |
| author |
Inchausti Vallés, Almudena |
| author_facet |
Inchausti Vallés, Almudena Mollfulleda, Rosa Swart, Marcel Perles Hernáez, Josefina Herrero Domínguez, Santiago García Baonza, Valentín Taravillo Corralo, Mercedes Lobato Fernández, Álvaro |
| author_role |
author |
| author2 |
Mollfulleda, Rosa Swart, Marcel Perles Hernáez, Josefina Herrero Domínguez, Santiago García Baonza, Valentín Taravillo Corralo, Mercedes Lobato Fernández, Álvaro |
| author2_role |
author author author author author author author |
| dc.contributor.none.fl_str_mv |
Universidad Complutense de Madrid |
| dc.subject.none.fl_str_mv |
546 Bidentate ligands Diruthenium Metal–metal bond Paddlewheel Electronic structure Ciencias 23 Química |
| topic |
546 Bidentate ligands Diruthenium Metal–metal bond Paddlewheel Electronic structure Ciencias 23 Química |
| description |
Previous studies on bimetallic paddlewheel compounds have established a direct correlation between metal–metal distance and ligand torsion angles, leading to the rule that higher torsion results in longer metal-metal bond distances. Here, the new discovery based on diarylformamidinate Ru₂⁵⁺ paddlewheel compounds [Ru2Cl(DArF)4] that show an opposite behavior is reported: higher torsions lead to shorter metal–metal distances. This discovery challenges the assumption that internal rotation solely impacts the δ bond. By combining experimental and theoretical techniques, it is demostrated that this trend is associated with previously overlooked π metal-ligand interactions. These π metal-ligand interactions are a direct consequence of the paddlewheel structure and the conjugated nature of the bidentate ligands. This findings offer far-reaching insights into the influence of equatorial ligands and their π-conjugation characteristics on the electronic properties of paddlewheel complexes. That this effect is not exclusive of diruthenium compounds but also occurs in other bimetallic cores such as ditungsten or dirhodium is demonstrated, and with other ligands showing allyl type conjugation. These results provide a novel approach for fine-tuning the properties of these compounds with significant implications for materials design. |
| publishDate |
2024 |
| dc.date.none.fl_str_mv |
2024 2024-07-03 2024 2024-07-03 |
| dc.type.none.fl_str_mv |
journal article http://purl.org/coar/resource_type/c_6501 VoR http://purl.org/coar/version/c_970fb48d4fbd8a85 |
| dc.type.openaire.fl_str_mv |
info:eu-repo/semantics/article |
| format |
article |
| dc.identifier.none.fl_str_mv |
https://hdl.handle.net/20.500.14352/113725 |
| url |
https://hdl.handle.net/20.500.14352/113725 |
| dc.language.none.fl_str_mv |
Inglés eng |
| language_invalid_str_mv |
Inglés |
| language |
eng |
| dc.rights.none.fl_str_mv |
open access http://purl.org/coar/access_right/c_abf2 Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ |
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info:eu-repo/semantics/openAccess |
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open access http://purl.org/coar/access_right/c_abf2 Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ |
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openAccess |
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application/pdf |
| dc.publisher.none.fl_str_mv |
Wiley |
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Wiley |
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reponame:Docta Complutense instname:Universidad Complutense de Madrid (UCM) |
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Universidad Complutense de Madrid (UCM) |
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Docta Complutense |
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Docta Complutense |
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