2026-04-04T02:26:42Zhttps://recercat.cat/oai/request

oai:recercat.cat:10256/282622026-02-08T00:43:55Zcom_2072_452955com_2072_2054col_2072_453073

Characterization of a Silver Vinylcarbene Intermediate in Carbene–Alkyne Metathesis and Its Concerted C(sp2)–H Bond Insertion Díaz Jiménez, Àlex Monreal Corona, Roger Saha, Arijit Álvarez Núñez, Andrea Company Casadevall, Anna Parella Coll, Teodor Pérez, Pedro J. Caballero Bevia, Ana Roglans i Ribas, Anna Poater Teixidor, Albert Pla i Quintana, Anna Agencia Estatal de Investigación Metàtesi (Química) Metathesis (Chemistry) Intermediaris (Química) Intermediates (Chemistry) Carbens Carbenes (Methylene compounds) Carboni -- Compostos Carbon compounds Hidrocarburs Hydrocarbons Plata Silver Herein we present compelling evidence of the intervention of electrophilic silver vinylcarbenes in the carbene-alkyne metathesis (CAM) reaction, leading to a pivotal C(sp2)-H insertion process. The delicate equilibrium between the stability and reactivity of transient species is crucial for efficient detection. Through meticulous mechanistic exploration, we unveil that the mechanism for the C(sp2)-H insertion hinges on the substitution pattern. Indeed, it departs from the previously documented stepwise mechanism (involving Wheland intermediates), and it follows a concerted route, quite uncommon for this transformation The authors are grateful for finantial support from Projects PID2021-127423NB-I00 to A.P., PID2020-113711GB-I00 and PID2023-146849NB-I00 to A.P.-Q., PID2019-106699GB-I00 to A.Co., PID2020-113797RB-C21 and PID2023-146946NB-I00 to P.J.P. and A.C. funded by the Ministerio de Ciencia, Innovación y Universidades of Spain MCIU/AEI/10.13039/501100011033 and FEDER, UE,; RED2022-134074-T and RED2022-134331-T for network support, and from the Generalitat de Catalunya (2021-SGR-623 to A.R., 2021SGR-475 to A.Co. projects). We thank the Spanish Ministerio de Universidades for the predoctoral fellowship FPU18/02912 to À.D.-J. and FPU20/00707 to R.M.-C. and the Catalan Government for the predoctoral fellowship 2022 FI_B 00605 to A.A.-N. and a Beatriu de Pinós-AGAUR Postdoctoral grant (2022BP00051) to A.S.. A.P.-Q., A. Co, and A.P. are Serra Húnter Fellows and A.P. and A.Co. thank ICREA Academia Prizes Open Access funding provided thanks to the CRUE-CSIC agreement with ACS 2026-01-12 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion peer-reviewed http://hdl.handle.net/10256/28262 http://hdl.handle.net/10256/28262 eng info:eu-repo/semantics/altIdentifier/doi/10.1021/jacs.5c19806 info:eu-repo/semantics/altIdentifier/issn/0002-7863 info:eu-repo/semantics/altIdentifier/eissn/1520-5126 PID2021-127423NB-I00 PID2020-113711GB-I00 PID2023-146849NB-I00 PID2019-106699GB-I00 info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-127423NB-I00/ES/CATALISIS PREDICTIVA PARA CAMBIAR EL ODEN SECUENCIAL ENTRE EXPERIMENTOS I CALCULOS/ info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-113711GB-I00/ES/DISEÑO Y SINTESIS DE FULLERENOS PARA LA CONSTRUCCION DE CELDAS SOLARES HIBRIDAS DE PEROVSKITA Y FULERENOS D ALTO RENDIMIENTO. UN ENFOQUE EXPERIMENTAL Y COMPUTACIONAL SINERGICO/ info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2023-146849NB-I00/ES/DESAFIOS Y OPORTUNIDADES EN EL CONTROL DE LA SELECTIVIDAD EN LA CICLACION DE ALENOS, FULLERENOS Y VINILCARBENOS CATALIZADA POR METALES DE TRANSICION/ info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-106699GB-I00/ES/LIGANDOS NO INOCENTES COMO PLATAFORMAS PARA LA FUNCIONALIZACION DE ENLACES C-H Y C=C CON GRUPOS OXO, NITRENO Y CARBENO/ Attribution 4.0 International http://creativecommons.org/licenses/by/4.0/ info:eu-repo/semantics/openAccess application/pdf American Chemical Society (ACS) Journal of the American Chemical Society (JACS), 2026, vol. 148, núm. 3, p. 3689-3696 Articles publicats (D-Q)