Well-Defined, Silica-Supported Homobimetallic Nickel Hydride Hydrogenation Catalyst.

There is an increasing interest to replace precious metal-based catalysts by earth-abundant nonprecious metals due to higher costs, toxicity, and declining availability of the former. Here, the synthesis of a well-defined supported nickel hydrogenation catalyst prepared by surface organometallic chemistry is reported. For this purpose, [LNi(μ-H)]2 (L = HC(CMeNC6H3(iPr)2)2) was grafted on partially dehydroxylated silica to give a homobimetallic H- and O(silica)-bridged Ni2 complex. The structure of the latter was confirmed by infrared spectroscopy, X-ray absorption near-edge structure, and extended X-ray absorption fine structure analyses as well as hydride titration studies. The immobilized catalyst was capable of hydrogenating alkenes and alkynes at low temperatures without prior activation. As an example, ethene can be hydrogenated with an initial turnover frequency of 25.5 min-1 at room temperature.