Alternative Conceptual Approach to the Design of Bifunctional Catalysts: An Osmium Germylene System for the Dehydrogenation of Formic Acid

[Image: see text] The reaction of the hexahydride OsH(6)(P(i)Pr(3))(2) with a P,Ge,P-germylene-diphosphine affords an osmium tetrahydride derivative bearing a Ge,P-chelate, which arises from the hydrogenolysis of a P–C(sp(3)) bond. This Os(IV)–Ge(II) compound is a pioneering example of a bifunctional catalyst based on the coordination of a σ-donor acid, which is active in the dehydrogenation of formic acid to H(2) and CO(2). The kinetics of the dehydrogenation, the characterization of the resting state of the catalysis, and DFT calculations point out that the hydrogen formation (the fast stage) exclusively occurs on the coordination sphere of the basic metal center, whereas both the metal center and the σ-donor Lewis acid cooperatively participate in the CO(2) release (the rate-determining step). During the process, the formate group pivots around the germanium to approach its hydrogen atom to the osmium center, which allows its transfer to the metal and the CO(2) release.