TIFR
Department of Chemical Sciences
School of Natural Sciences

December 7, 2017 at 2.30 pm in B-333

Title :

Energy Relevant Processes Catalyzed by Corrole Metal Complexes

Abstract:

We have recently introduced corrole metal complexes (metallocorroles) as catalysts for various energy-relevant reactions. This includes those that are of prime importance for the electrochemical splitting of water into its elements, as well as the hydrogen and oxygen evolution reactions. Tuning of the redox potentials, M(I)/M(II) for proton reduction, M(II)/M(III) for oxygen reduction, and M(III)/M(IV)/M(V) for water oxidation (M= Fe, Co, or Mn), is achieved via variations of substituents on the corrole ligand. Practical catalysis is achieved via immobilization onto carbon electrodes, while mechanism-of-action insight is obtained by performing homogenous catalysis and characterization of reaction intermediates. The thus achieved conclusions are used for hypothesis-driven changes in the catalyst’s structures as to achieve the desired properties required for optimal catalytic efficacy and selectivity. This will be demonstrated by the introduction of newly developed catalysts with trifluoromethyl substituents.

 

REFERENCES:

 

•"Metallocorroles as photocatalysts for driving endergonic reactions, exemplified by bromide to bromine conversion", Angew. Chem. 2015, 54, 12370 –12373.

•"Metallocorroles as Non-Precious Metal Catalysts for Oxygen Reduction", Angew. Chem. 2015, 54, 14080 –14084.

•“Metallocorroles as Non-Precious Metal Electrocatalysts for Highly Efficient Oxygen Reduction in Alkaline Media" ChemCatChem 2016, 8, 2832-2837.

•“Metallocorroles as Electrocatalysts for the Oxygen Reduction Reaction (ORR)", Israel J. Chem. 2016, 56, 756– 762 (invited review).

•“Dioxygen bound Cobalt Corroles”, Chem. Commun. 2017, 53, 877-880.

•“Selective CF3 Substitution for Affecting the Physical and Chemical Properties of Gold Corroles” Angew. Chem. 2017, 56, 9837-9841.

•“Corroles as Triplet Photosensitizers”, Coord. Chem. Rev. 2017, 0000.

•“One-pot synthesis of contracted and expanded porphyrins with meso-CF3 groups, from affordable precursors” Angew. Chem. 2017, 56, 0000.