Direct Heterogenization of Salphen Coordination Complexes to Porous Organic Polymers: Catalysts for Ring-Expansion Carbonylation of Epoxides.

Salen and salphens are important ligands in coordination chemistry due to their ability to form various metal complexes that can be used for a variety of organic transformations. However, salen/salphen complexes are difficult to separate from the reaction mixture, thereby limiting their application to homogeneous systems. Accordingly, considerable effort has been spent to heterogenize the metallosalen/salphen complexes; however, this has resulted in compromised activities and selectivities. Direct heterogenization of metallosalens to form porous organic polymers (POPs) shows promise for heterogeneous catalysis, because it would allow easy separation while retaining catalytic function. Thus, a facile synthetic strategy for preparing metallosalen/salphen-based porous organic polymers through direct molecular knitting using a Friedel-Crafts reaction is presented herein for the first time. As representative candidates, salphenM(III)Cl (M = Al3+ and Cr3+) complexes are knitted by covalent cross-linking using this facile, scalable, one-pot method to synthesize highly POPs in high yields. When incorporated with [Co(CO)4]- anions, the resulting heterogeneous Lewis acidic metal (Al3+ and Cr3+) POPs exhibit propylene oxide ring-expansion carbonylation activity on par with those of their homogeneous counterparts.