RT Journal Article
T1 Alkanes C1–C6 C–H Bond Activation via a Barrierless Potential Energy Path: Trifluoromethyl Carbenes Enhance Primary C–H Bond Functionalization
A1 Martínez Laguna, Jonathan
A1 Altarejos, Julia
A1 Fuentes Domínguez, María Ángeles
A1 Sciortino, Giuseppe
A1 Maseras, Feliu
A1 Carreras, Javier
A1 Caballero Bevia, Ana
A1 Pérez Romero, Pedro José
AB In this mixed computational and experimental study, we report a catalytic system for alkane C1–C6 functionalization in which the responsible step for C–H bond activation shows no barrier in the potential energy path. DFT modeling of three silver-based catalysts and four diazo compounds led to the conclusion that the TpFAg=C(H)CF3 (TpF = fluorinated trispyrazolylborate ligand) carbene intermediates interact with methane without a barrier in the potential energy surface, a prediction validated by experimentation using N2=C(H)CF3 as the carbene source. The array of alkanes from propane to n-hexane led to the preferential functionalization of the primary sites with unprecedented values of selectivity for an acceptor diazo compound. The lack of those barriers implies that selectivity can no longer be controlled by differences in the energy barriers. Molecular dynamics calculations (with propane as the model alkane) are consistent with the preferential functionalization of the primary sites due to a higher concentration of such C–H bonds in the vicinity of the carbenic carbon atom.
PB American Chemical Society
SN 0002-7863
SN 1520-5126 (electrónico)
YR 2024
FD 2024-11
LK https://hdl.handle.net/10272/24671
UL https://hdl.handle.net/10272/24671
LA eng
NO Martínez-Laguna, J., Altarejos, J., Fuentes, M. Á., Sciortino, G., Maseras, F., Carreras, J., Caballero, A., & Pérez, P. J. (2024). Alkanes C1–C6 C–H Bond Activation via a Barrierless Potential Energy Path: Trifluoromethyl Carbenes Enhance Primary C–H Bond Functionalization. In Journal of the American Chemical Society (Vol. 146, Issue 49, pp. 34014–34022). American Chemical Society (ACS). https://doi.org/10.1021/jacs.4c13065
NO We thank the Ministerio de Ciencia e Innovación for GrantsPID2020-113797RB-C21, TED2021-130077B−I00, PID2020-112825RB-I00, CES2019-000925-S, PID2019-105007GA-I00,CNS2022-135208 and RED2022-134074-T. We also thank Universidad de Huelva (P.O. Feder UHU-202024) and CERCA Programme/Generalitat de Catalunya. We also thank funding for open access publication to Universidad de Huelva / CBUA.
DS Repositorio Institucional de la Universidad de Huelva
RD 14 jul 2026