Metal−Organic Framework‐Induced Rh Monocoodination on Diphosphine Ligand Enables Catalytic Hydroformylation of Aliphatic Olefins at Room Temperature and Pressure

Abstract Persistent challenges in hydroformylation of olefins include controlling regioselectivity, particularly for short aliphatic olefins and conducting reactions under ambient conditions. We report here the synthesis of monophosphine–Rh complexes on a typical chelated diphosphine ligand mediated by a Zr‐MOF through isolating a pair of phosphorus atoms. We demonstrate that single‐crystal X‐ray diffraction can elucidate the structural transformation of the Rh catalyst during olefin hydroformylation, providing valuable information on active site reconstruction during catalysis. The Rh‐MOF catalyst demonstrates excellent catalytic and recyclable performance in the hydroformylation of short aliphatic olefins with linear to branched ratios of up to 99 : 1. Due to the framework‘s capacity to adsorb and concentrate gases, the catalytic reactions occur under room temperature and pressure, eliminating the need for the high temperature and pressures typically required in homogeneous systems. This study show that Zr–MOF can be a unique platform for synthesizing unusual catalytic species that cannot exist in solutions for meaningful chemical transformations and elucidate valuable structural information pertaining to metal‐based catalysis.