A High-Valent Ru-PCP Pincer Catalyst for Hydrosilylation Reactions

In this communication, we report on successfully applying a high-valent Ru(IV) bifunctional catalyst (1) for the hydrosilylation of carbonyl compounds, carboxylic acids, esters, nitriles, and nitroarenes. We found that high-valent hydride complexes can be regarded as “hard” nucleophiles, unlike more conventional low-valent counterparts. They demonstrate high chemoselectivity and affinity to reducing polar bonds over nonpolar ones. The scope and limitations of the method, as well as the plausible mechanism of the reaction, are described.