Artículo
σ-Silane Platinum(II) Complexes as Intermediates in C−Si Bond-Coupling Processes
Autor/es | Ríos Moreno, Pablo
Fouilloux, Hugo Díez, Josefina Vidossich, Pietro Lledós, Agustí Conejero Iglesias, Salvador |
Departamento | Universidad de Sevilla. Departamento de Química Inorgánica |
Fecha de publicación | 2019 |
Fecha de depósito | 2022-10-05 |
Publicado en |
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Resumen | Platinum complexes [Pt(NHC’)(NHC)][BArF] (NHC’
denotes the cyclometallated N-heterocyclic carbene ligand, NHC)
react with primary silanes RSiH3 leading to the cyclometallated
platinum(II) silyl complexes [Pt(NHC-SiHR’ ... Platinum complexes [Pt(NHC’)(NHC)][BArF] (NHC’ denotes the cyclometallated N-heterocyclic carbene ligand, NHC) react with primary silanes RSiH3 leading to the cyclometallated platinum(II) silyl complexes [Pt(NHC-SiHR’)(NHC)][BArF] through a process that involves the formation of C−Si and Pt−Si bonds with concomitant extrusion of H2. Low temperature NMR studies indicate that the process proceeds with the initial formation of the σ-SiH complexes [Pt(NHC’)(NHC)(HSiH2R][BArF] which are stable at temperatures below 0 °C. At higher temperatures activation of one Si−H bond followed by a C−Si coupling reaction generates an agostic SiH platinum hydride derivative [Pt(H)(NHC’- SiH2R)(NHC)][BArF] that undergoes a second SiH bond activation producing the final products. Computational modelling of the reaction mechanism indicate that the stereochemistry of the silyl/hydride ligands after the first Si−H bond cleavage dictates the nature of the products, favoring the formation of a C−Si bond over C−H, in contrast to previous results observed with tertiary silanes. Furthermore, the process involves a trans to cis isomerization of the NHC ligands before the second Si−H bond cleavage |
Agencias financiadoras | Ministerio de Economía y Competitividad (MINECO). España European Commission (EC). Fondo Europeo de Desarrollo Regional (FEDER) Junta de Andalucía |
Identificador del proyecto | CTQ2016-76267-P
CTQ2017-87889-P CTQ2016-81797-REDC FQM-2126 |
Cita | Ríos Moreno, P., Fouilloux, H., Díez, J., Vidossich, P., Lledós, A. y Conejero Iglesias, S. (2019). σ-Silane Platinum(II) Complexes as Intermediates in C−Si Bond-Coupling Processes. Chemistry - A European Journal, 25 (48), 11346-11355. https://doi.org/10.1002/chem.201902226. |
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