By Roman Boulatov (auth.), José H. Zagal, Fethi Bedioui, Jean-Pol Dodelet (eds.)

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"This is a superb and designated publication of 14 chapters that's well timed in its reports of the electrochemical and electrocatalytic houses of the porphyrinoids and is written by way of a number specialists within the diverse fields lined. … this is often an exhilarating publication to learn. it'd be a very valuable booklet to have within the laboratory library. The chapters are unique and informative with very good tables and figures … ." (Martin Stillman, magazine of the yankee Chemical Society, Vol. 129 (5), 2007)

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The degradation of the catalytic properties of these complexes during turnover is also fairly quick for industrial applications. 1. mV (at pH 7) using Fe porphyrin complexes in physical contact with an electrode. Arguably, a monometallic catalyst is easier to design and synthesize than a bimetallic one. The only structural feature of the heme/Cu site that appears to be critical is an axial ligation of Fe by imidazole or possibly pyridine. For this ligand to effectively compete with H2 O for Fe coordination, it must be covalently attached to the porphyrin in the appropriate (chelating) conformation.

Studies of biomimetic respiratory O2 reduction aim at: (a) designing small synthetic catalysts for electrochemical reduction of O2 at biologically relevant electrochemical potentials (>50 mV vs. NHE) and in a neutral aqueous medium with the turnover frequency and the selectivity of HCOs and (b) using these catalysts to clarify the structure/activity relationship at the O2 -reducing heme/Cu site of HCOs. The best biomimetic catalysts reproduce key kinetic and mechanistic aspects of O2 reduction by HCOs, but fall short of HCOs in their turnover frequencies at potentials >50 mV.

For this ligand to effectively compete with H2 O for Fe coordination, it must be covalently attached to the porphyrin in the appropriate (chelating) conformation. 18) can be achieved by introducing the Cu ion. It is unclear if the improvements of this magnitude justify the synthetic effort required to create a tris-imidazole superstructure. We lack sufficient understanding of Fe-porphyrin-based reduction of O2 to predict what, if any, groups can replace imidazoles to yield easier-to-synthesize and oxidatively more stable catalysts without diminishing their catalytic properties.

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