Gold (I) complexes bearing monophosphole ligands were synthesized, and their electronic and steric properties were compared to those of their triphenylphosphine-based counterparts. Cationic phosphole-based gold (I) complexes are active and selective in enyne cycloisomerization and in olefin cyclopropanation, with a good correlation between the ligand σ-donor ability and the catalytic activity. For the most efficient ligand, 1-phenyl-2 ...