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Updated: Jun 23, 2025

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Published on: October 5, 2019
Dioxygen Activation by Gold(I)-Distorted Porphyrin Dinuclear Complexes
Wataru Suzuki1,2, Yoshiyuki Mizuhata1,3,4, Norihiro Tokitoh1,3,4
1Institute for Chemical Research, Kyoto University, Gokasho Uji, Kyoto, 611-0011, Japan.
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.
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