Threefold reactivity of a COF-embedded rhenium catalyst: reductive etherification, oxidative esterification or transfer hydrogenation.

The reactivity of the novel Re(I) catalyst [Re( C12 Anth-py 2 )(CO) 3 Br] is modulated by its interactions with the covalent organic framework (COF) TFB-BD. The complex catalyzes either reductive etherification, oxidative esterification, or transfer hydrogenation depending on its local environment (embedded in TFB-BD, in homogeneous solution or co-incubated with TFB-BD, respectively). The results highlight that COFs can drastically modulate the reactivity of homogeneous catalysts.