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. Author manuscript; available in PMC: 2019 Nov 28.
Published in final edited form as: Chem Rev. 2018 Oct 29;118(22):10840–11022. doi: 10.1021/acs.chemrev.8b00074

Figure 93.

Figure 93.

(A) Noodleman and co-workers,909,917 computational structure depicting the key hydroperoxo bridged hemea3-CuB complex (with a proton derived from Y237 on the heme distal O-atom) which will now undergo O–O reductive cleavage following electron-transfer from the deprotonated Y237 phenol. This could be intermediate IP (Scheme 23). (B) Computational structure from Karlin and co-workers919 of a synthetic (porphryinate)FeIII-(μ-O22–)-CuII construct where the heme distal peroxo O atom is H-bonded to an exogenous phenol (p-nitrophenol), poised to undergo O–O reductive cleavage, as described in sections 5.2.6.