RT Journal Article
T1 Methane Catalytic Amidation via a Plausible Copper-Nitrene Intermediate
A1 Martínez Laguna, Jonathan
A1 Cholewinska, Anna
A1 Borrego, Elena
A1 Besora, María
A1 Álvarez, María
A1 Caballero Bevia, Ana
A1 Pérez Romero, Pedro José
AB The catalytic conversion of CH4 into CH3X compounds has been reported in a few cases, usually involving dehydrogenative processes in which the H atom is lost. Aiming at expanding this limited set of transformations, we have investigated the methane amidation reaction through metal-catalyzed nitrene transfer reactions, a transformation that remains unreported to date for the lightest hydrocarbon. Herein, we describe the use of copper-based catalysts for the direct, nondehydrogenative amidation reaction of methane via a metal-mediated formal nitrene insertion into the C−H bond, a reaction that is also extended to the series of gaseous alkanes. Mechanistic studies, supported by DFT calculations, a microkinetic model, and experimental evidence have led to the proposal of a metallonitrene intermediate responsible for this C−H amidation process via sequential hydrogen abstraction and rebound steps.
PB American Chemical Society
SN 0002-7863
SN 1520-5126 (electrónico)
YR 2026
FD 2026
LK https://hdl.handle.net/10272/28207
UL https://hdl.handle.net/10272/28207
LA eng
NO Martínez-Laguna, J., Cholewinska, A., Borrego, E., Besora, M., Álvarez, M., Caballero, A., & Pérez, P. J. (2026). Methane Catalytic Amidation via a Plausible Copper-Nitrene Intermediate. Journal of the American Chemical Society, 148(8), 9057–9065. https://doi.org/10.1021/jacs.5c22747
NO We thank the Spanish Ministerio de Ciencia e Innovación for grants TED 2021-130077B-100 (PJP), PID2020-113797RB-C21 (PJP, AC), PID2023-146946NB-I00 (PJP), RED2022-134074-T (PJP), CN2022-136079 (MB), PID2021-128188NB-100 (MB), and the Catalan Agency for Research (AGAUR) 021 SGR 00110 (MB). We also thank Universidad de Huelva/CBUA for open access charges.
DS Repositorio Institucional de la Universidad de Huelva
RD 28 may 2026