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Título: | Hydrosilylation of terminal alkynes catalyzed by a ONO-pincer iridium(III) hydride compound: Mechanistic insights into the hydrosilylation and dehydrogenative silylation catalysis |
Autor: | Pérez-Torrente, Jesús J. CSIC ORCID; Nguyen, Duc H.; Jiménez, M. Victoria CSIC ORCID ; Modrego, Francisco J. CSIC ORCID; Puerta-Oteo, Raquel CSIC; Gómez-Bautista, Daniel CSIC ORCID; Iglesias, Manuel CSIC ORCID; Oro, Luis A. CSIC ORCID | Fecha de publicación: | 2016 | Editor: | American Chemical Society | Citación: | Organometallics 35(14): 2410-2422 (2016) | Resumen: | The catalytic activity in the hydrosilylation of terminal alkynes by the unsaturated hydrido iridium(III) compound [IrH(κ-hqca)(coe)] (1), which contains the rigid asymmetrical dianionic ONO pincer ligand 8-oxidoquinoline-2-carboxylate, has been studied. A range of aliphatic and aromatic 1-alkynes has been efficiently reduced using various hydrosilanes. Hydrosilylation of the linear 1-alkynes hex-1-yne and oct-1-yne gives a good selectivity toward the β-(Z)-vinylsilane product, while for the bulkier t-Bu-C≡CH a reverse selectivity toward the β-(E)-vinylsilane and significant amounts of alkene, from a competitive dehydrogenative silylation, has been observed. Compound 1, unreactive toward silanes, reacts with a range of terminal alkynes RC≡CH, affording the unsaturated η-alkenyl complexes [Ir(κ-hqca)(E-CH=CHR)(coe)] in good yield. These species are able to coordinate monodentate neutral ligands such as PPh and pyridine, or CO in a reversible way, to yield octahedral derivatives. Further mechanistic aspects of the hydrosilylation process have been studied by DFT calculations. The catalytic cycle passes through Ir(III) species with an iridacyclopropene (η-vinylsilane) complex as the key intermediate. It has been found that this species may lead both to the dehydrogenative silylation products, via a β-elimination process, and to a hydrosilylation cycle. The β-elimination path has a higher activation energy than hydrosilylation. On the other hand, the selectivity to the vinylsilane hydrosilylation products can be accounted for by the different activation energies involved in the attack of a silane molecule at two different faces of the iridacyclopropene ring to give η-vinylsilane complexes with either an E or Z configuration. Finally, proton transfer from a η-silane to a η-vinylsilane ligand results in the formation of the corresponding β-(Z)- and β-(E)-vinylsilane isomers, respectively. | Versión del editor: | https://doi.org/10.1021/acs.organomet.6b00471 | URI: | http://hdl.handle.net/10261/154892 | DOI: | 10.1021/acs.organomet.6b00471 | Identificadores: | doi: 10.1021/acs.organomet.6b00471 e-issn: 1520-6041 issn: 0276-7333 |
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