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Crystal structures of the copper(II) complex I and dimeric copper-(II) complex J of the hydroxylated ligand 2a (Scheme 3) have been reported in ref 22.
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Direct injection of a concentrated solution of the Cu(I) starting materials into the solvent saturated with dioxygen at the low temperature may remove the lag phase observed in Figure 3, enabling us to detect the initially formed Cu(I)-superoxo intermediate (Scheme 4). However, the limited solubility of the Cu(I) starting materials in THF has precluded doing this experiment.
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2-binding at higher temperature (>-40 °C).
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The electron-donating substituent would increase the d-π interaction between the copper center and the benzene ring, which may prevent the interaction of the copper center with dioxygen by a steric hindrance. Details about such interaction in the copper complexes will be reported elsewhere.
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In this paper, the monomeric species formed from the peroxo intermediate by O-O bond homolysis is described as Cu(II)-O·, although another canonical form Cu(III)=O is also possible. In the present system, however, we could not characterize such a monomeric copper-oxygen species, since it is just a transient reactive intermediate, if it is formed.
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78
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2-peroxodicopper(II) species.
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