Abstract
Strategies towards the synthesis of palladium(II), rhodium(I) and iridium(I) complexes bearing O‐functionalized triazolylidene ligands are reported. Mono‐ and dimetallic triazolylidene palladium complexes with ether, acetate, and hydroxy functionalities were synthesized using silver transmetalation. Selective formation of either the mono‐ or dimetallic palladium chlorido complexes was controlled by the amount of NMe4Cl used as an auxiliary in the metalation step, as excess halide traps the palladium precursor as unreactive palladate [PdCl4]2–. Analogous rhodium(I) and iridium(I) complexes with ether and acetate substituents were accessible by a silver transmetalation protocol, while alkoxide‐tethered triazolylidene complexes required base‐mediated metalation procedures. The alkoxide‐functionalized C,O‐bidentate chelating triazolylidene ligand is hemilabile and metalacycle opening and closing is triggered by the presence of acid and base, respectively. Such ligand versatility is attractive for bond activation catalysis.
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