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https://doi.org/10.1021/acs.inorgchem.2c04166
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Título: | Reductive Elimination Reactions in Gold(III) Complexes Leading to C(sp3)–X (X = C, N, P, O, Halogen) Bond Formation: Inner-Sphere vs SN2 Pathways |
Fecha de publicación: | 19-ene-2023 |
Fecha de defensa / creación: | 2022 |
Editorial: | American Chemical Society |
Cita bibliográfica: | Inorganic Chemistry, 2023, vol. 62, issue 4, pag. 1708-1718 |
ISSN: | Electronic: 1520-510X Print: 0947-6539 |
Materias relacionadas: | CDU::5 - Ciencias puras y naturales::54 - Química::546 - Química inorgánica |
Palabras clave: | Gold Alkyls Dissociation Reductive elimination Nucleophilic Substitution |
Resumen: | The reactions leading to the formation of C–heteroatom bonds in the coordination sphere of Au(III) complexes are uncommon, and their mechanisms are not well known. This work reports on the synthesis and reductive elimination reactions of a series of Au(III) methyl complexes containing different Au–heteroatom bonds. Complexes [Au(CF3)(Me)(X)(PR3)] (R = Ph, X = OTf, OClO3, ONO2, OC(O)CF3, F, Cl, Br; R = Cy, X = Me, OTf, Br) were obtained by the reaction of trans-[Au(CF3)(Me)2(PR3)] (R = Ph, Cy) with HX. The cationic complex cis-[Au(CF3)(Me)(PPh3)2]OTf was obtained by the reaction of [Au(CF3)(Me)(OTf)(PPh3)] with PPh3. Heating these complexes led to the reductive elimination of MeX (X = Me, Ph3P+, OTf, OClO3, ONO2, OC(O)CF3, F, Cl, Br). Mechanistic studies indicate that these reductive elimination reactions occur either through (a) the formation of tricoordinate intermediates by phosphine dissociation, followed by reductive elimination of MeX, or (b) the attack of weakly coordinating anionic (TfO– or ClO4–) or neutral nucleophiles (PPh3 or NEt3) to the Au-bound methyl carbon. The obtained results show for the first time that the nucleophilic substitution should be considered as a likely reductive elimination pathway in Au(III) alkyl complexes. |
Autor/es principal/es: | Portugués, Alejandro Martínez-Nortes, Miguel Ángel Bautista, Delia González-Herrero, Pablo Gil-Rubio, Juan |
Facultad/Departamentos/Servicios: | Facultades, Departamentos, Servicios y Escuelas::Departamentos de la UMU::Química Inorgánica |
Versión del editor: | https://pubs.acs.org/doi/10.1021/acs.inorgchem.2c04166 |
URI: | http://hdl.handle.net/10201/137770 |
DOI: | https://doi.org/10.1021/acs.inorgchem.2c04166 |
Tipo de documento: | info:eu-repo/semantics/article |
Número páginas / Extensión: | 35 |
Derechos: | info:eu-repo/semantics/openAccess Atribución 4.0 Internacional |
Descripción: | © 2023. The authors. This document is made available under the CC-BY 4.0 license http://creativecommons.org/licenses/by /4.0/ This document is the submitted version of a published work that appeared in final form in Inorganic Chemistry. |
Aparece en las colecciones: | Artículos: Química Inorgánica |
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Fichero | Descripción | Tamaño | Formato | |
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Au-red-elim_IC.pdf | 3,69 MB | Adobe PDF | Visualizar/Abrir |
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