RT info:eu-repo/semantics/article
T1 Identity of the Silyl Ligand in an Iron Silyl Complex Influences Olefin Hydrogenation: An Experimental and Computational Study
A1 Najera, Daniel C.
A1 Peñas de Frutos, Marconi Nicolás
A1 García Melchor, Max
A1 Fout, Alison R.
K1 Química
K1 Sililo de hierro
K1 Olefinas
K1 Hidrogenación
K1 23 Química
AB In this study, we explore the selective synthesis of iron silyl complexes using the reaction of an iron mesityl complex (MesCCC)FeMes(Py) with various hydrosilanes. These resulting iron silyl complexes,(MesCCC)Fe(SiH2Ph)(Py)(N2), (MesCCC)-Fe(SiMe2Ph)(Py)(N2), and (MesCCC)Fe[SiMe(OSiMe3)2](Py)-(N2), serve as effective precatalysts for olefin hydrogenation. The key to their efficiency in catalysis lies in the specific nature of the silyl ligand attached to the iron center. Experimental observations,supported by density functional theory (DFT) simulations, reveal that the catalytic performance correlates with the relative stability of dihydrogen and hydride species associated with each iron silyl complex. The stability of these intermediates is crucial for efficient hydrogen transfer during the catalytic cycle. The DFT simulations help to quantify these stability factors, showing a direct relationship between the silyl ligand’s electronic and steric properties and the overall catalytic activity. Complexes with certain silyl ligands exhibit better performance due to the optimal balance between the stability and reactivity of the key active catalyst. This work highlights the importance of ligand design in the development of ironbased hydrogenation catalysts.
PB American Chemical Society
SN 0020-1669
YR 2024
FD 2024
LK https://uvadoc.uva.es/handle/10324/69742
UL https://uvadoc.uva.es/handle/10324/69742
LA eng
NO Inorganic Chemistry, Septiembre 2024
NO Producción Científica
DS UVaDOC
RD 24-dic-2024