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 documento: | Artículo |
| Fecha de publicación: | 2024 |
| País: | España |
| Institución: | Universidad Complutense de Madrid (UCM) |
| Repositorio: | Docta Complutense |
| Lenguaje: | Inglés |
| OAI Identifier: | oai:docta.ucm.es:20.500.14352/113725 |
| Acceso en línea: | https://hdl.handle.net/20.500.14352/113725 |
| Nivel de acceso: | Acceso abierto |
| Palabra clave: | 546 Bidentate ligands Diruthenium Metal–metal bond Paddlewheel Electronic structure Ciencias 23 Química |
| _version_ | 1878733012558938112 |
|---|---|
| author | Inchausti Vallés, Almudena |
| 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 |
| author_browse | García Baonza, Valentín Herrero Domínguez, Santiago Inchausti Vallés, Almudena Lobato Fernández, Álvaro Mollfulleda, Rosa Perles Hernáez, Josefina Swart, Marcel Taravillo Corralo, Mercedes |
| 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 |
| collection | Docta Complutense |
| 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. |
| eu_rights_str_mv | openAccess |
| format | article |
| id | ES_4e5c8c3e94d56767b5bbe21d50cb9b8e |
| institution | Universidad Complutense de Madrid (UCM) |
| instname_str | Universidad Complutense de Madrid (UCM) |
| language | eng |
| network_acronym_str | ES |
| network_name_str | España |
| oai_identifier_str | oai:docta.ucm.es:20.500.14352/113725 |
| publishDate | 2024 |
| publishDateSort | 2024 |
| publisher | Wiley |
| publisherStr | Wiley |
| reponame_str | Docta Complutense |
| spelling | Torsion Effects Beyond the δ Bond and the Role of π Metal-Ligand Interactions Inchausti Vallés, Almudena Mollfulleda, Rosa Swart, Marcel Perles Hernáez, Josefina Herrero Domínguez, Santiago García Baonza, Valentín Taravillo Corralo, Mercedes Lobato Fernández, Álvaro 546 Bidentate ligands Diruthenium Metal–metal bond Paddlewheel Electronic structure Ciencias 23 Química 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. Wiley https://hdl.handle.net/20.500.14352/113725 |
| 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 | 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_short | 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 |
| topic | 546 Bidentate ligands Diruthenium Metal–metal bond Paddlewheel Electronic structure Ciencias 23 Química |
| topic_facet | 546 Bidentate ligands Diruthenium Metal–metal bond Paddlewheel Electronic structure Ciencias 23 Química |
| url | https://hdl.handle.net/20.500.14352/113725 |