Experimental and Computational Studies on the Catalytic and Luminescent Properties of Ni, Pd and Au Complexes with 2-Chalcone or 2-Biaryl Phosphines
The work developed in this Thesis entails the design and synthesis of new phosphine ligands. These phosphines show either a 2-chalcone or a 2-biaryl moiety, where their fluorination degree modulates their electronic properties. The new ligands have been employed in different systems in combination w...
| Autor: | |
|---|---|
| Tipo de recurso: | tesis doctoral |
| Estado: | Versión publicada |
| Fecha de publicación: | 2023 |
| País: | España |
| Institución: | Universidad de Valladolid |
| Repositorio: | UVaDOC. Repositorio Documental de la Universidad de Valladolid |
| OAI Identifier: | oai:uvadoc.uva.es:10324/61067 |
| Acceso en línea: | https://doi.org/10.35376/10324/61067 https://uvadoc.uva.es/handle/10324/61067 |
| Access Level: | acceso abierto |
| Palabra clave: | Química inorgánica Catalysis Catálisis Phosphines Fosfinas Organometallic Organometálica 2303 Química Inorgánica |
| id |
ES_3121bd8a3ca07dfbaa2a3dd1cb8573fb |
|---|---|
| oai_identifier_str |
oai:uvadoc.uva.es:10324/61067 |
| network_acronym_str |
ES |
| network_name_str |
España |
| repository_id_str |
|
| dc.title.none.fl_str_mv |
Experimental and Computational Studies on the Catalytic and Luminescent Properties of Ni, Pd and Au Complexes with 2-Chalcone or 2-Biaryl Phosphines |
| title |
Experimental and Computational Studies on the Catalytic and Luminescent Properties of Ni, Pd and Au Complexes with 2-Chalcone or 2-Biaryl Phosphines |
| spellingShingle |
Experimental and Computational Studies on the Catalytic and Luminescent Properties of Ni, Pd and Au Complexes with 2-Chalcone or 2-Biaryl Phosphines Ponce de León Pintado, Jaime Química inorgánica Catalysis Catálisis Phosphines Fosfinas Organometallic Organometálica 2303 Química Inorgánica |
| title_short |
Experimental and Computational Studies on the Catalytic and Luminescent Properties of Ni, Pd and Au Complexes with 2-Chalcone or 2-Biaryl Phosphines |
| title_full |
Experimental and Computational Studies on the Catalytic and Luminescent Properties of Ni, Pd and Au Complexes with 2-Chalcone or 2-Biaryl Phosphines |
| title_fullStr |
Experimental and Computational Studies on the Catalytic and Luminescent Properties of Ni, Pd and Au Complexes with 2-Chalcone or 2-Biaryl Phosphines |
| title_full_unstemmed |
Experimental and Computational Studies on the Catalytic and Luminescent Properties of Ni, Pd and Au Complexes with 2-Chalcone or 2-Biaryl Phosphines |
| title_sort |
Experimental and Computational Studies on the Catalytic and Luminescent Properties of Ni, Pd and Au Complexes with 2-Chalcone or 2-Biaryl Phosphines |
| dc.creator.none.fl_str_mv |
Ponce de León Pintado, Jaime |
| author |
Ponce de León Pintado, Jaime |
| author_facet |
Ponce de León Pintado, Jaime |
| author_role |
author |
| dc.contributor.none.fl_str_mv |
Espinet Rubio, Pablo Universidad de Valladolid. Escuela de Doctorado |
| dc.subject.none.fl_str_mv |
Química inorgánica Catalysis Catálisis Phosphines Fosfinas Organometallic Organometálica 2303 Química Inorgánica |
| topic |
Química inorgánica Catalysis Catálisis Phosphines Fosfinas Organometallic Organometálica 2303 Química Inorgánica |
| description |
The work developed in this Thesis entails the design and synthesis of new phosphine ligands. These phosphines show either a 2-chalcone or a 2-biaryl moiety, where their fluorination degree modulates their electronic properties. The new ligands have been employed in different systems in combination with transition metals in order to study different topics such as metal-ligand interactions, reaction mechanism, catalysis or luminescent properties. The 2-chalcone phosphines (PEWO) have been identified as excellent promoters of the reductive elimination step both with Ni and Pd. This ability has been exploited to develop a Negishi catalysis to synthetize symmetric and non-symmetric highly fluorinated biaryls under mild conditions with excellent yields and great selectivity. The selectivity of this process can be further enhanced by means of a bimetallic Pd/Cu system, due to the in situ generation of the nucleophile in catalytic concentrations. The development of these two catalytic systems encouraged us to design new Pd complexes with partially fluorinated aryls that could act as efficient precatalysts with easy activation. PEWO ligands, as well as some of their Pd complexes, also exhibit luminescent properties due to the fluorinated 2-chalcone moiety they have in their structure. 2-biarylphosphines have been employed to analyze the metal-ligand interaction in [AuCl(L)] complexes in combined experimental and computational studies. These phosphines also show a peculiar cyclization reaction that implies an intramolecular SNAr reaction between the P atom and the ortho C–F bond of the lower aryl, leading to luminescent fluorophosphoranes. |
| publishDate |
2023 |
| dc.date.none.fl_str_mv |
2023 |
| dc.type.none.fl_str_mv |
info:eu-repo/semantics/doctoralThesis info:eu-repo/semantics/publishedVersion |
| format |
doctoralThesis |
| status_str |
publishedVersion |
| dc.identifier.none.fl_str_mv |
https://doi.org/10.35376/10324/61067 https://uvadoc.uva.es/handle/10324/61067 |
| url |
https://doi.org/10.35376/10324/61067 https://uvadoc.uva.es/handle/10324/61067 |
| dc.language.none.fl_str_mv |
Inglés |
| language_invalid_str_mv |
Inglés |
| dc.rights.none.fl_str_mv |
info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by-nc-nd/4.0/ |
| eu_rights_str_mv |
openAccess |
| rights_invalid_str_mv |
http://creativecommons.org/licenses/by-nc-nd/4.0/ |
| dc.format.none.fl_str_mv |
application/pdf |
| dc.source.none.fl_str_mv |
reponame:UVaDOC. Repositorio Documental de la Universidad de Valladolid instname:Universidad de Valladolid |
| instname_str |
Universidad de Valladolid |
| reponame_str |
UVaDOC. Repositorio Documental de la Universidad de Valladolid |
| collection |
UVaDOC. Repositorio Documental de la Universidad de Valladolid |
| repository.name.fl_str_mv |
|
| repository.mail.fl_str_mv |
|
| _version_ |
1869405590817603584 |
| spelling |
Experimental and Computational Studies on the Catalytic and Luminescent Properties of Ni, Pd and Au Complexes with 2-Chalcone or 2-Biaryl PhosphinesPonce de León Pintado, JaimeQuímica inorgánicaCatalysisCatálisisPhosphinesFosfinasOrganometallicOrganometálica2303 Química InorgánicaThe work developed in this Thesis entails the design and synthesis of new phosphine ligands. These phosphines show either a 2-chalcone or a 2-biaryl moiety, where their fluorination degree modulates their electronic properties. The new ligands have been employed in different systems in combination with transition metals in order to study different topics such as metal-ligand interactions, reaction mechanism, catalysis or luminescent properties. The 2-chalcone phosphines (PEWO) have been identified as excellent promoters of the reductive elimination step both with Ni and Pd. This ability has been exploited to develop a Negishi catalysis to synthetize symmetric and non-symmetric highly fluorinated biaryls under mild conditions with excellent yields and great selectivity. The selectivity of this process can be further enhanced by means of a bimetallic Pd/Cu system, due to the in situ generation of the nucleophile in catalytic concentrations. The development of these two catalytic systems encouraged us to design new Pd complexes with partially fluorinated aryls that could act as efficient precatalysts with easy activation. PEWO ligands, as well as some of their Pd complexes, also exhibit luminescent properties due to the fluorinated 2-chalcone moiety they have in their structure. 2-biarylphosphines have been employed to analyze the metal-ligand interaction in [AuCl(L)] complexes in combined experimental and computational studies. These phosphines also show a peculiar cyclization reaction that implies an intramolecular SNAr reaction between the P atom and the ortho C–F bond of the lower aryl, leading to luminescent fluorophosphoranes.El trabajo desarrollado en esta Tesis implica el diseño y síntesis de nuevos ligandos fosfina. Estas fosfinas presentan un grupo 2-chalcona o 2-biarilo en su estructura, donde su grado de fluoración modula sus propiedades electrónicas. Los nuevos ligandos han sido empleados en distintos sistemas en combinación con metales de transición para abordar diversas temáticas como las interacciones metal-ligando, mecanismos de reacción, catálisis o propiedades luminiscentes. Las fosfinas derivadas de 2-chalcona (PEWO) han sido identificadas como excelentes promotores de la etapa de eliminación reductora tanto en Ni como en Pd. Esta habilidad ha sido explotada para desarrollar una catálisis de tipo Negishi para la síntesis de biarilos altamente fluorados tanto simétricos como asimétricos en condiciones de reacción suaves, con rendimientos excelentes y alta selectividad. La selectividad de este proceso puede ser incrementada aún más mediante un sistema bimetálico Pd/Cu, gracias a la generación in situ del nucleófilo en concentraciones catalíticas. El desarrollo de estos dos sistemas catalíticos nos animó a diseñar nuevos complejos de Pd con arilos parcialmente fluorados que actuasen como precatalizadores de activación fácil altamente eficientes. Los ligandos PEWO, al igual que alguno de sus complejos de Pd, también presentan propiedades luminiscentes debido a la presencia del grupo 2-chalcona fluorado en su estructura. Las fosfinas 2-biarílicas han sido utilizadas para analizar las interacciones metal-ligando en complejos [AuCl(L)] mediante la combinación de estudios experimentales y teóricos. Estas fosfinas también presentan una peculiar reacción de ciclación que implica una reacción SNAr intramolecular entre el átomo de fósforo y el enlace C–F en posición orto del arilo inferior, generando fluorofosforanos luminiscentes.Escuela de DoctoradoDoctorado en Química: Química de Síntesis, Catálisis y Materiales AvanzadosEspinet Rubio, PabloUniversidad de Valladolid. Escuela de Doctorado2023info:eu-repo/semantics/doctoralThesisinfo:eu-repo/semantics/publishedVersionapplication/pdfhttps://doi.org/10.35376/10324/61067https://uvadoc.uva.es/handle/10324/61067reponame:UVaDOC. Repositorio Documental de la Universidad de Valladolidinstname:Universidad de ValladolidInglésinfo:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-nd/4.0/oai:uvadoc.uva.es:10324/610672026-06-13T12:44:47Z |
| score |
15.300724 |