Autor según el artículo: Alvarez, Maria; Besora, Maria; Molina, Francisco; Maseras, Feliu; Belderrain, Tomas R.; Perez, Pedro J.;
Departamento: Química Física i Inorgànica
e-ISSN: 1520-5126
Autor/es de la URV: Besora Bonet, Maria
Palabras clave: Transition metals Synthesis (chemical) Simultaneous observation Reagent Organic synthesis Organic compounds Microkinetic models Metal complexes Metal complex Metal carbenes Ligands Ligand Kinetics Hydrogen bond Hydrogen Diazo compounds Dft calculation Density functional theory Decarbonylations Decarbonylation Copper compounds Copper Chemical modification Carbon monoxide Carbon Carbene insertion Carbene Calculation Article
Resumen: Many transition-metal complexes MLn decompose diazo compounds N-2=(CRR2)-R-1 generating metal-carbenes LnM=(CRR2)-R-1 which transfer the carbene group to other substrates, constituting an important tool in organic synthesis. All previous reports have shown that the (CRR2)-R-1 fragment at the metal-carbene remains intact from the parent diazo compound. Herein we report the detection and isolation of a monosubstituted copper carbene where the (CRR2)-R-1 ligand has undergone a modification from the initial diazo reagent. When Tp(Ms)Cu(THF) (Tp(Ms) = hydrotris(3-mesityl)pyrazolylborate ligand) was reacted with N,N-diethyl diazoacetamide [N-2=C(H)(CONEt2)], the stable copper carbene Tp(Ms)Cu=C(H)(NEt2) was isolated, resulting from a decarbonylation process, with carbon monoxide being trapped as Tp(Ms)Cu(CO). The simultaneous observation of products derived from the intramolecular carbene insertion reaction into C-H bonds demonstrates that the expected Tp(Ms)Cu=C(H)(CONEt2) complex is also formed. Experimental data, DFT calculations, and microkinetic models allow us to propose that the latter undergoes CO loss en route to the former.
Áreas temáticas: Química Materiais Interdisciplinar General chemistry Farmacia Engenharias iv Engenharias iii Engenharias ii Colloid and surface chemistry Ciências biológicas ii Ciências biológicas i Ciências agrárias i Ciência de alimentos Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Chemistry Catalysis Biochemistry Astronomia / física
Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
ISSN: 0002-7863
Direcció de correo del autor: maria.besora@urv.cat
Identificador del autor: 0000-0002-6656-5827
Fecha de alta del registro: 2023-02-19
Versión del articulo depositado: info:eu-repo/semantics/acceptedVersion
Enlace a la fuente original: https://pubs.acs.org/doi/10.1021/jacs.1c01483
URL Documento de licencia: http://repositori.urv.cat/ca/proteccio-de-dades/
Referencia al articulo segun fuente origial: Journal Of The American Chemical Society. 143 (12): 4837-4843
Referencia de l'ítem segons les normes APA: Alvarez, Maria; Besora, Maria; Molina, Francisco; Maseras, Feliu; Belderrain, Tomas R.; Perez, Pedro J.; (2021). Two Copper-Carbenes from One Diazo Compound. Journal Of The American Chemical Society, 143(12), 4837-4843. DOI: 10.1021/jacs.1c01483
DOI del artículo: 10.1021/jacs.1c01483
Entidad: Universitat Rovira i Virgili
Año de publicación de la revista: 2021
Tipo de publicación: Journal Publications
Repositori URV