O2 Reduction Reaction by Biologically Relevant Anionic Ligand Bound Iron Porphyrin Complexes

2013 ◽  
Vol 52 (22) ◽  
pp. 12963-12971 ◽  
Author(s):  
Subhra Samanta ◽  
Pradip Kumar Das ◽  
Sudipta Chatterjee ◽  
Kushal Sengupta ◽  
Biswajit Mondal ◽  
...  
Keyword(s):  
Reduction Reaction ◽  
Iron Porphyrin ◽  
Biologically Relevant ◽  
Anionic Ligand ◽  
O2 Reduction ◽  
Iron Porphyrin Complexes

Tuning the thermodynamic onset potential of electrocatalytic O2 reduction reaction by synthetic iron–porphyrin complexes

2015 ◽  
Vol 51 (49) ◽  
pp. 10010-10013 ◽  
Author(s):  
Sk Amanullah ◽  
Pradip Kumar Das ◽  
Subhra Samanta ◽  
Abhishek Dey
Keyword(s):  
Reduction Reaction ◽  
Iron Porphyrin ◽  
Onset Potential ◽  
Porphyrin Ligand ◽  
O2 Reduction ◽  
Iron Porphyrin Complexes

A porphyrin ligand with two β-pyrrolic electron withdrawing ester groups is synthesized and its Co complex is crystallographically characterized.

Effect of axial ligands on electronic structure and O2 reduction by iron porphyrin complexes: Towards a quantitative understanding of the "push effect"

2015 ◽  
Vol 19 (01-03) ◽  
pp. 92-108 ◽  
Author(s):  
Subhra Samanta ◽  
Pradip Kumar Das ◽  
Sudipta Chatterjee ◽  
Abhishek Dey
Keyword(s):  
Electronic Structure ◽  
Active Sites ◽  
Reduction Reaction ◽  
Axial Ligand ◽  
Iron Porphyrin ◽  
Axial Ligands ◽  
O2 Reduction ◽  
Thiolate Complexes ◽  
Quantitative Understanding ◽  
Iron Porphyrin Complexes

Axial ligands play a dominating role in determining the electronic structure and reactivity of iron porphyrin active sites and synthetic models. Several properties unique to the cysteine bound heme enzyme, cytochrome P450, is attributed to the "push effect" of the thiolate axial ligand. In this mini-review the ground state electronic structure of iron porphyrins with imidazole, phenolate and thiolate complexes, derived using a combination of spectroscopy and DFT calculations, are discussed. The differences in kinetics and selectivity of oxygen reduction reaction (ORR), catalyzed by these iron porphyrin complexes with different axial ligands, help elucidate the varying push effects of the different axial ligands on oxygen activation by ferrous porphyrin. The spectroscopic and kinetic data help to develop a quantitative understanding of the "push effect" and, in particular, the electrostatic and covalent contributions to it.

scholarly journals Combining scaling relationships overcomes rate versus overpotential trade-offs in O2 molecular electrocatalysis

2020 ◽  
Vol 6 (11) ◽  
pp. eaaz3318 ◽  
Author(s):  
Daniel J. Martin ◽  
Brandon Q. Mercado ◽  
James M. Mayer
Keyword(s):  
Energy Efficiency ◽  
Reaction Rate ◽  
Electrical Energy ◽  
Reduction Reaction ◽  
Iron Porphyrin ◽  
Scaling Relationships ◽  
Anionic Ligand ◽  
Trade Offs ◽  
Rate Versus ◽  
Molecular Catalysts

The development of advanced chemical-to-electrical energy conversions requires fast and efficient electrocatalysis of multielectron/multiproton reactions, such as the oxygen reduction reaction (ORR). Using molecular catalysts, correlations between the reaction rate and energy efficiency have recently been identified. Improved catalysis requires circumventing the rate versus overpotential trade-offs implied by such “scaling relationships.” Described here is an ORR system—using a soluble iron porphyrin and weak acids—with the best reported combination of rate and efficiency for a soluble ORR catalyst. This advance is achieved not by “breaking” scaling relationships but rather by combining two of them. Key to this behavior is a polycationic ligand, which enhances anionic ligand binding and changes the catalyst E1/2. These results show how combining scaling relationships is a powerful way toward improved electrocatalysis.

Concerted Proton–Electron Transfer in Electrocatalytic O2 Reduction by Iron Porphyrin Complexes: Axial Ligands Tuning H/D Isotope Effect

2015 ◽  
Vol 54 (5) ◽  
pp. 2383-2392 ◽  
Author(s):  
Sudipta Chatterjee ◽  
Kushal Sengupta ◽  
Subhra Samanta ◽  
Pradip Kumar Das ◽  
Abhishek Dey
Keyword(s):  
Electron Transfer ◽  
Isotope Effect ◽  
Iron Porphyrin ◽  
Axial Ligands ◽  
O2 Reduction ◽  
Iron Porphyrin Complexes

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

2019 ◽  
Vol 10 (42) ◽  
pp. 9692-9698 ◽  
Author(s):  
Arnab Ghatak ◽  
Snehadri Bhakta ◽  
Sarmistha Bhunia ◽  
Abhishek Dey
Keyword(s):  
Reduction Reaction ◽  
Iron Porphyrin ◽  
Iron Porphyrins ◽  
Guanidine Group ◽  
O2 Reduction

The O2 reduction reaction (ORR) catalysed by iron porphyrins with covalently attached pendant guanidine groups is reported.

Aliphatic hydroxylation catalyzed by iron porphyrin complexes

1983 ◽  
Vol 105 (20) ◽  
pp. 6243-6248 ◽  
Author(s):  
John T. Groves ◽  
Thomas E. Nemo
Keyword(s):  
Iron Porphyrin ◽  
Iron Porphyrin Complexes

High-valent iron-porphyrin complexes related to peroxidase and cytochrome P-450

1981 ◽  
Vol 103 (10) ◽  
pp. 2884-2886 ◽  
Author(s):  
John T. Groves ◽  
Robert C. Haushalter ◽  
Mikio Nakamura ◽  
Thomas E. Nemo ◽  
B. J. Evans
Keyword(s):  
Iron Porphyrin ◽  
Iron Porphyrin Complexes ◽  
High Valent ◽  
Cytochrome P 450
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