@article{10272/24671,
year = {2024},
month = {11},
url = {https://hdl.handle.net/10272/24671},
abstract = {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.},
organization = {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.},
publisher = {American Chemical Society},
title = {Alkanes C1–C6 C–H Bond Activation via a Barrierless Potential Energy Path: Trifluoromethyl Carbenes Enhance Primary C–H Bond Functionalization},
doi = {10.1021/jacs.4c13065},
author = {Martínez Laguna, Jonathan and Altarejos, Julia and Fuentes Domínguez, María Ángeles and Sciortino, Giuseppe and Maseras, Feliu and Carreras, Javier and Caballero Bevia, Ana and Pérez Romero, Pedro José},
}