Rhodium Hydrogenation Catalysts Supported in Metal Organic Frameworks: Influence of the Framework on Catalytic Activity and Selectivity

The cationic rhodium complexes (dppe)­Rh­(COD)­BF₄ and (MeCN)₂Rh­(COD)­BF₄ have been supported in metal–organic frameworks bearing anionic nodes (ZJU-28) and anionic linkers (MIL-101-SO₃) via ion exchange. These MOF-supported Rh species serve as recyclable catalysts for the hydrogenation of both the terminal alkene substrate 1-octene and the internal alkene substrate 2,3-dimethylbutene. The nature of the MOF support impacts various aspects of catalysis, including: (i) the rate of 1-octene hydrogenation, (ii) the activity and recyclability of the catalyst in 2,3-dimethylbutene hydrogenation, and (iii) the size selectivity of hydrogenation with alkene substrates appended to calixarenes.