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oai:uvadoc.uva.es:10324/697422025-03-26T19:10:04Zcom_10324_28542com_10324_952com_10324_894col_10324_28543

Najera, Daniel C. Peñas de Frutos, Marconi Nicolás García Melchor, Max Fout, Alison R. 2024-09-13T07:50:41Z 2024-09-13T07:50:41Z 2024 Inorganic Chemistry, Septiembre 2024 0020-1669 https://uvadoc.uva.es/handle/10324/69742 10.1021/acs.inorgchem.4c02533 Producción Científica 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. A.R.F. and D.C.N. thank NSF CHE 232496 and PD Soros for funding. We also acknowledge the DJEI/DES/SFI/HEA Irish Centre for High-End Computing (ICHEC) for the provision of computational resources. M.N.P.D. thanks the UVa for a Margarita Salas fellowship (ref CONVREC-2021-221). application/pdf eng American Chemical Society info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/4.0/ Attribution-NonCommercial-NoDerivatives 4.0 Internacional Química Sililo de hierro Olefinas Hidrogenación 23 Química Identity of the Silyl Ligand in an Iron Silyl Complex Influences Olefin Hydrogenation: An Experimental and Computational Study info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion https://pubs.acs.org/doi/10.1021/acs.inorgchem.4c02533?ref=PDF SI