Publication: 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
| dc.contributor.author | Portugués Rodríguez, Alejandro | |
| dc.contributor.author | Martínez-Nortes, Miguel Ángel | |
| dc.contributor.author | Bautista, Delia | |
| dc.contributor.author | González Herrero, Pablo | |
| dc.contributor.author | Gil Rubio, Juan | |
| dc.contributor.department | Química Inorgánica | |
| dc.date.accessioned | 2024-01-25T11:37:56Z | |
| dc.date.available | 2024-01-25T11:37:56Z | |
| dc.date.copyright | © 2023 The Authors | |
| dc.date.issued | 2023-01-19 | |
| dc.description.abstract | 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. | es |
| dc.format | application/pdf | es |
| dc.format.extent | 35 | es |
| dc.identifier.citation | Inorganic Chemistry, 2023, vol. 62, issue 4, pag. 1708-1718 | |
| dc.identifier.doi | https://doi.org/10.1021/acs.inorgchem.2c04166 | |
| dc.identifier.issn | Electronic: 1520-510X | |
| dc.identifier.issn | Print: 0947-6539 | |
| dc.identifier.uri | http://hdl.handle.net/10201/137770 | |
| dc.language | eng | es |
| dc.publisher | American Chemical Society | es |
| dc.relation | PROYECTO 1) Ministerio de Ciencia e Innovación/FEDER (Proyectos de I+D de Generación de Conocimiento 2018; nombre del proyecto: "Ampliando la aplicabilidad de los complejos organometálicos de metales de transición en catálisis y fotoquímica"; referencia PGC2018-100719-B-100). PROYECTO 2) Agencia de Ciencia y Tecnología de la Región de Murcia, Fundación Séneca (Ayudas a Grupos de Excelencia 2014; nombre del proyecto: "Síntesis, estructura y reactividad de nuevos tipos de complejos organometálicos. Aplicaciones como intermedios en síntesis y materiales fotoactivos", referencia 19890/GERM/15) . | es |
| dc.relation | Financial support from the following grants is gratefully acknowledged: grant PGC2018-100719-B-I00 funded by MCIN/AEI/10.13039/501100011033 and by ERDF A way of making Europe; grant 19890/GERM/15 funded by the Séneca Foundation of the Region of Murcia (Ayudas a Grupos de Excelencia). | |
| dc.relation.publisherversion | https://pubs.acs.org/doi/10.1021/acs.inorgchem.2c04166 | es |
| dc.rights | info:eu-repo/semantics/openAccess | es |
| dc.rights | Atribución 4.0 Internacional | * |
| dc.rights.uri | http://creativecommons.org/licenses/by/4.0/ | * |
| dc.subject | Gold | es |
| dc.subject | Alkyls | es |
| dc.subject | Dissociation | es |
| dc.subject | Reductive elimination | es |
| dc.subject | Nucleophilic Substitution | es |
| dc.subject.other | CDU::5 - Ciencias puras y naturales::54 - Química::546 - Química inorgánica | es |
| dc.title | 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 | es |
| dc.type | info:eu-repo/semantics/article | es |
| dc.type.version | info:eu-repo/semantics/acceptedVersion | |
| dspace.entity.type | Publication | es |
| relation.isAuthorOfPublication | 244828c8-5381-49a7-9972-c550880196e5 | |
| relation.isAuthorOfPublication | 940323e4-526b-4ee9-b4f9-728b2b9a5da7 | |
| relation.isAuthorOfPublication | 2f3d3cfa-1196-4adc-8012-a11c570cafc4 | |
| relation.isAuthorOfPublication.latestForDiscovery | 244828c8-5381-49a7-9972-c550880196e5 |
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