Impact of Linker Engineering on the Catalytic Activity of Metal-Organic Frameworks Containing Pd(II)-Bipyridine Complexes

A series of mixed-linker bipyridyl metal organic framework (MOF)-supported palladium(II) catalysts were used to elucidate the electronic and steric effects of linker substitution on the activity of these catalysts in the context of Suzuki Miyaura 60. cross-coupling reactions. m-6,6'-Me(2)bpy-MOF-PdCl2 exhibited 110- and 496-fold enhancements in activity compared to nonfunctionalized m-bpy-MOF-PdCl2 and m-4,4'-Me(2)bpy-MOE-PdCl2, respectively. This result clearly demonstrates that the stereoelectronic properties of metal-binding linker units are critical to the activity of single-site organometallic catalysts in MOFs and highlights the importance of linker engineering in the design and development of efficient MOF catalysts.