The bimetallic rhodium(II) paddlewheel (Rh2A4) complex is one of the most reactive classes of rhodium catalysts, well-renowned for the most demanding carbene- and nitrene-transfer reactions. In view of its importance in modern synthetic chemistry, we herein report a facile approach for preparing a self-supported and reusable dirhodium(II) polymer-based heterogeneous catalyst through a reductive ligation protocol. The catalyst displays good reactivity for inter- and intramo-lecular nitrene- and carbene-insertions of various olefins, and can also engage in C–H insertion of hydrocarbon deriva-tives, all under ambient conditions. The increased catalyst reusability is expected to empower the use of these precious metal catalysts at industrial scales.
Contains experimental procedures and spectral data.