Au(III) π‐Allyl Complexes: Synthesis, Structure, Reactivity, and Catalytic Applications

π‐Allyl complexes of transition metals are key species in organometallic chemistry and homogeneous catalysis. Palladium(II) π‐allyl complexes in particular, have gained a lot of attention, but their isoelectronic gold(III) counterparts long remained elusive. However, this situation changed during the last few years. This concept article describes the preparative routes, characterization, structure and reactivity of such species, together with their catalytic applications. The influence of the ancillary ligand at gold, either (P,C)/(N,C)‐cyclometalated or (P,N)‐hemilabile, is analysed in detail. The Au(III) and Pd(II) π‐allyl complexes are also compared to highlight the similarities and differences. Au(III) π‐allyl complexes have recently been shown to be readily accessible and stable, as well as highly reactive towards nucleophiles, including in catalytic transformations. They display structural features and reactivity profiles that differ noticeably from the related Pd(II) π‐allyl complexes, making them complementary and attractive for synthesis.