Metal-Organic Frameworks Stabilize Mono(phosphine)-Metal Complexes for Broad-Scope Catalytic Reactions

Mono(phosphine)-M (M-PR3; M = Rh and Ir) complexes selectively prepared by postsynthetic metalation of a porous triarylphosphine-based metal-organic framework (MOP) exhibited excellent activity in the hydrosilylation of ketones and alkenes, the hydrogenation of alkenes, and the C-H borylation of arenes. The recyclable and reusable MOF catalysts significantly outperformed their homogeneous counterparts, presumably via stabilizing M-PR3 intermediates by preventing deleterious disproportionation reactions/ligand exchanges in the catalytic cycles.