The structures and spectroscopic properties of well-characterized copper-dioxygen complexes were analyzed. The ligand attributes that create O 2-reactive Cu(I) complexes and lead to specific types of Cu/O 2 species were discussed. It was shown that prevalent formation of dimeric Cu/O 2 complexes in homogeneous solutions is consistent with the thermodynamic trends of O 2 reduction. The results show that most Cu/O 2 reactions generate a thermodynamic rather than a kinetic Cu/O 2 product.
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