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

The catalytic activity in the hydrosilylation of terminal alkynes by the unsaturated hydrido iridium(III) compound [IrH(κ 3 -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 1 -alkenyl complexes [Ir(κ 3 -hqca)( E -CH═CHR)(coe)] in good yield. These species are able to coordinate monodentate neutral ligands such as PPh 3 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 2 -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 1 -vinylsilane complexes with either an E or Z configuration. Finally, proton transfer from a η 2 -silane to a η 1 -vinylsilane ligand results in the formation of the corresponding β-( Z )- and β-( E )-vinylsilane isomers, respectively.