Wataru Suzuki

Abstract Interactions between gold‐based materials and dioxygen (O₂) have motivated researchers to understand reaction mechanisms for O₂ activation by homo‐ and heterogeneous gold catalysts. In this work, gold(I) porphyrin dinuclear complexes were synthesized with a saddle‐distorted porphyrin ligand. The gold(I) porphyrin complexes showed unprecedented O₂ activation in the presence of protic solvents to form gold(III) tetradentate porphyrin complexes. Mechanistic insights into the O₂ activation by the gold(I) center were elucidated by spectroscopic measurements and theoretical calculations, revealing that dissociation of halides on the gold(I) center by alcohol solvents and hydrogen bonding of an N−H proton in the distorted porphyrin with dioxygen played important roles in establishing the unique reactivities of gold(I) complexes.