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Influence of the distal guanidine group on the rate and selectivity of O2 reduction by iron porphyrin

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Abstract

The O2 reduction reaction (ORR) catalysed by iron porphyrins with covalently attached pendant guanidine groups is reported. The results show a clear enhancement in the rate and selectivity for the 4e/4H+ ORR. In situ resonance Raman investigations show that the rate determining step (rds) is O2 binding to ferrous porphyrins in contrast to the case of mononuclear iron porphyrins and heme/Cu analogues where the O–O bond cleavage of a heme peroxide is the rds. The selectivity is further enhanced when an axial imidazole ligand is introduced. Thus, the combination of the axial imidazole ligand and pendant guanidine ligand, analogous to the active site of peroxidases, is determined to be very effective in enabling a facile and selective 4e/4H+ ORR.

Graphical abstract: Influence of the distal guanidine group on the rate and selectivity of O2 reduction by iron porphyrin

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Publication details

The article was received on 04 Jun 2019, accepted on 28 Aug 2019 and first published on 29 Aug 2019


Article type: Edge Article
DOI: 10.1039/C9SC02711D
Chem. Sci., 2019, Advance Article
  • Open access: Creative Commons BY-NC license
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    Influence of the distal guanidine group on the rate and selectivity of O2 reduction by iron porphyrin

    A. Ghatak, S. Bhakta, S. Bhunia and A. Dey, Chem. Sci., 2019, Advance Article , DOI: 10.1039/C9SC02711D

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