Self-Supported Heterogeneous Dirhodium(II) Catalyst for Nitrene and Carbene Transfer Reactions

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 intramolecular nitrene- and carbene-insertions of various olefins, and can also engage in C-H insertion of hydrocarbon derivatives, all under ambient conditions. The catalyst reusability is expected to empower the use of these precious metal catalysts at industrial scales.