Hydrogenation of -Heteroarenes Using Rhodium Precatalysts: Reductive Elimination Leads to Formation of Multimetallic Clusters.

A rhodium-catalyzed method for the hydrogenation of -heteroarenes is described. A diverse array of unsubstituted -heteroarenes including pyridine, pyrrole, and pyrazine, traditionally challenging substrates for hydrogenation, were successfully hydrogenated using the organometallic precatalysts, [(η-CMe)Rh(N-C)H] (N-C = 2-phenylpyridinyl (ppy) or benzo[]quinolinyl (bq)). In addition, the hydrogenation of polyaromatic -heteroarenes exhibited uncommon chemoselectivity. Studies into catalyst activation revealed that photochemical or thermal activation of [(η-CMe)Rh(bq)H] induced C(sp)-H reductive elimination and generated the bimetallic complex, [(η-CMe)Rh(μ,η-bq)Rh(η-CMe)H]. In the presence of H, both of the [(η-CMe)Rh(N-C)H] precursors and [(η-CMe)Rh(μ,η-bq)Rh(η-CMe)H] converted to a pentametallic rhodium hydride cluster, [(η-CMe)RhH], the structure of which was established by NMR spectroscopy, X-ray diffraction, and neutron diffraction. Kinetic studies on pyridine hydrogenation were conducted with each of the isolated rhodium complexes to identify catalytically relevant species. The data are most consistent with hydrogenation catalysis prompted by an unobserved multimetallic cluster with formation of [(η-CMe)RhH] serving as a deactivation pathway.