A Novel M ₈ L ₆ Cubic Cage That Binds Tetrapyridyl Porphyrins: Cage and Solvent Effects in Cobalt?Porphyrin?Catalyzed Cyclopropanation Reactions

Confinement of a catalyst can have significant impact on catalytic performance and lead to otherwise difficult achieve properties. Herein, we report the design synthesis novel caged system Co?G@Fe8(Zn?L ? 1)6, which is soluble in both polar apolar solvents without necessity any post-functionalization. This rare example metal-coordination cage able bind catalytically active porphyrins that spanning wide variety polarity. was used investigate combined effects solvent cobalt catalyzed cyclopropanation styrene, involves radical intermediates. Kinetic studies show DMF has protective influence catalyst, slowing down deactivation [Co(TPP)] leading higher TONs this solvent. Moreover, DFT rate determining energy barrier radical-type transformation not influenced by coordination DMF. As such, increased obtained experimentally stem from stabilizing effect are due an intrinsic activity caused axial ligand binding center ([Co(TPP)(L)]). Remarkably, encapsulation Co?G led three times more than (TOFini) substantially TON compared free Co?G. The local concentration substrates hydrophobic bulk explains observed activities.