Influence of Hemilabile Arm and Amide Functionality in the Ligand Backbone on Chemical and Electrochemical Dioxygen Reduction Catalyzed by Mononuclear Copper(II) Complexes DOI
Abhishek Das, Srijan Narayan Chowdhury, Sachidulal Biswas

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 5, 2025

Four mononuclear copper(II) complexes, [(DPA-OH)Cu(CH3OH)(ClO4)](ClO4) (1), [(DPA-OMe)Cu(CH3OH)(ClO4)](ClO4) (2), [(6-Amide-DPA-OMe)Cu](ClO4)2 (3) and [(6-Amide2-DPA-OMe)Cu](ClO4)2 (4), of flexidentate ligands bearing hemilabile (hydroxy)methoxyethyl and/or amide group on DPA (di(2-picolyl)amine) backbone were isolated to explore their potency in catalyzing chemical electrochemical oxygen reduction reaction (ORR). The role a arm, as well functionality the ligand affecting rate-determining step (RDS) overall catalytic cycle has been explored compared with that analogous [(tmpa)Cu](ClO4)2 (tmpa = tris(2-pyridylmethyl)amine) [(PV-tmpa)Cu](ClO4)2 (PV-tmpa bis(pyrid-2-ylmethyl){[6-(pivalamido)pyrid-2-yl]methyl}-amine) complexes. arm these complexes results an third-order rate, kcat values ranging from 103 104 M-2s-1 during dioxygen catalysis. All except complex 4 selectively reduce via 4e-/4H+ pathway water (H2O) using decamethylferrocene (Fc*) sacrificial reductant acidic acetone at 298 K. In contrast, altering conditions ambiance phosphate buffer displays reverse order ORR activity while maintaining same product selectivity observed catalysis acetone.

Language: Английский

Influence of Hemilabile Arm and Amide Functionality in the Ligand Backbone on Chemical and Electrochemical Dioxygen Reduction Catalyzed by Mononuclear Copper(II) Complexes DOI
Abhishek Das, Srijan Narayan Chowdhury, Sachidulal Biswas

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 5, 2025

Four mononuclear copper(II) complexes, [(DPA-OH)Cu(CH3OH)(ClO4)](ClO4) (1), [(DPA-OMe)Cu(CH3OH)(ClO4)](ClO4) (2), [(6-Amide-DPA-OMe)Cu](ClO4)2 (3) and [(6-Amide2-DPA-OMe)Cu](ClO4)2 (4), of flexidentate ligands bearing hemilabile (hydroxy)methoxyethyl and/or amide group on DPA (di(2-picolyl)amine) backbone were isolated to explore their potency in catalyzing chemical electrochemical oxygen reduction reaction (ORR). The role a arm, as well functionality the ligand affecting rate-determining step (RDS) overall catalytic cycle has been explored compared with that analogous [(tmpa)Cu](ClO4)2 (tmpa = tris(2-pyridylmethyl)amine) [(PV-tmpa)Cu](ClO4)2 (PV-tmpa bis(pyrid-2-ylmethyl){[6-(pivalamido)pyrid-2-yl]methyl}-amine) complexes. arm these complexes results an third-order rate, kcat values ranging from 103 104 M-2s-1 during dioxygen catalysis. All except complex 4 selectively reduce via 4e-/4H+ pathway water (H2O) using decamethylferrocene (Fc*) sacrificial reductant acidic acetone at 298 K. In contrast, altering conditions ambiance phosphate buffer displays reverse order ORR activity while maintaining same product selectivity observed catalysis acetone.

Language: Английский

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