σ-Silane Platinum(II) Complexes as Intermediates in C−Si Bond-Coupling Processes
| Autor: | Josefina Díez, Pietro Vidossich, Hugo Fouilloux, Salvador Conejero, Agustí Lledós, Pablo Ríos |
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| Přispěvatelé: | Universidad de Sevilla. Departamento de Química Inorgánica, Ministerio de Economía y Competitividad (MINECO). España, European Commission (EC). Fondo Europeo de Desarrollo Regional (FEDER), Junta de Andalucía |
| Rok vydání: | 2019 |
| Předmět: |
Agostic interaction
010405 organic chemistry Ligand Hydride Organic Chemistry chemistry.chemical_element General Chemistry 010402 general chemistry 01 natural sciences Medicinal chemistry Catalysis Coupling reaction 0104 chemical sciences chemistry.chemical_compound chemistry Platinum Carbene Isomerization Bond cleavage |
| Zdroj: | Digital.CSIC. Repositorio Institucional del CSIC instname |
| Popis: | 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 Ministerio de Economía y Competitividad de España (MINECO) y Fondos europeos aportación FEDER-CTQ2016-76267-P, CTQ2017-87889-P y CTQ2016- 81797-REDC Junta de Andalucía-FQM-2126 |
| Databáze: | OpenAIRE |
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