A series of allyl (1–3) and cinnamyl (4–6) palladium(II) complexes supported by hydroxyl functionalized triazolylidenes have been prepared. All new compounds were fully characterized by means of 1H and 13C NMR spectroscopy, FT‐IR and elemental analyses. The new triazolylidene palladium complexes were tested as precatalysts in the coupling of aryl chlorides with boronic acids and the coupling of esters with amines to produce biphenyls and amides, respectively. According to the overall results, complexes 4 and 5 displayed the highest catalytic activity in both coupling processes, providing good to excellent yields under mild reaction conditions and using a wide range of substrates.

We report the straightforward synthesis and full characterization of a novel series rhodium(I) complexes (3 a-c) supported by hydroxyl-functionalized 1,2,3-triazolylidenes. All new compounds were fully characterized by means of 1 H and 13 C NMR spectroscopy, melting points, and elemental analyses. The new triazolylidene rhodium complexes 3 a-c were tested as catalysts in the hydrosilylation of terminal alkynes and the 1,4-addition of boronic acid to 2-cyclohexenone. Both catalytic processes provide good to excellent yields under low catalyst loadings and in the case of the hydrosilylation, a good selectivity toward the E-isomer is observed.