Hydrosilylation of Terminal Alkynes Catalyzed by a ONO-Pincer Iridium(III) Hydride Compound: Mechanistic Insights into the Hydrosilylation and Dehydrogenative Silylation Catalysis

• Published in: Organometallics Vol. 35; no. 14; pp. 2410 - 2422
• Main Authors: Pérez-Torrente, Jesús J, Nguyen, Duc Hanh, Jiménez, M. Victoria, Modrego, F. Javier, Puerta-Oteo, Raquel, Gómez-Bautista, Daniel, Iglesias, Manuel, Oro, Luis A
• Format: Journal Article
• Language: English
• Published: American Chemical Society 25.07.2016
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/acs.organomet.6b00471

The catalytic activity in the hydrosilylation of terminal alkynes by the unsaturated hydrido iridium­(III) compound [IrH­(κ3-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 η1-alkenyl complexes [Ir­(κ3-hqca)­(E-CHCHR)­(coe)] in good yield. These species are able to coordinate monodentate neutral ligands such as PPh3 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 (η2-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 η1-vinylsilane complexes with either an E or Z configuration. Finally, proton transfer from a η2-silane to a η1-vinylsilane ligand results in the formation of the corresponding β-(Z)- and β-(E)-vinylsilane isomers, respectively.