Dioxygen Reduction at a Cu(I) Complex Supported by a Macrocyclic N3O Ligand System
- 1Humboldt‐Universität Zu Berlin Institut Für Chemie Berlin Germany
- 2Technische Universität Institut Für Chemie Fakultät II Berlin Germany
Abstract
CuI(14 TMCO) (1), involving a N3O‐macrocycle, reacts with O2 at cryogenic temperatures to yield an end‐on peroxodicopper(II) species. The N4‐analogue CuI(14‐TMC) (2) remains unreactive under similar conditions. 2 contains an average short Cu─N bond length, resulting in a dominating trans‐effect, which inhibits O2 binding. In contrast, an elongated Cu─OTMCO bond trans to the O2‐binding site in 1 allows O2‐coordination. The catalytic reduction of O2 to H2O undergoes a full 4e−/4H+ process in 1. Notably, [CuI(12‐TMC)]+ (3), involving a smaller N4‐macrocycle where the Cu(I) ion is forced to move out of the plane formed by the four nitrogen atoms, also binds O2. However, in contrast to 1, 3 mediates the catalytic 2e−/2H+ reduction of O2 to H2O2 via two ligand‐assisted protonation steps. In this case, the reduction of O2 involves the initial formation of a side‐on peroxodicopper(II) species, where the weak Cu─Operoxo bond distance resulting from the strong σ‐donation from the trans Cu─N bond presumably leads to the release of H2O2 upon protonation. The present study provides deep mechanistic insights into the transition metal‐mediated O2 reduction process and reveals how the first coordination sphere can be tuned to control the 2e−/2H+ versus 4e−/4H+ reductions of O2.
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BibTeX
@article{schutze2026dioxygen,
title = {{Dioxygen Reduction at a Cu(I) Complex Supported by a Macrocyclic N3O Ligand System}},
author = {Maximilian Schütze and Dibya Jyoti Barman and Christian Lorent and Kallol Ray},
journal = {Chemistry (Weinheim an Der Bergstrasse, Germany)},
year = {2026},
month = aug,
doi = {10.1002/chem.71479},
url = {https://doi.org/10.1002/chem.71479},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Dioxygen Reduction at a Cu(I) Complex Supported by a Macrocyclic N3O Ligand System
AU - Maximilian Schütze
AU - Dibya Jyoti Barman
AU - Christian Lorent
AU - Kallol Ray
PY - 2026
DA - 2026/08/14
JO - Chemistry (Weinheim an Der Bergstrasse, Germany)
DO - 10.1002/chem.71479
UR - https://doi.org/10.1002/chem.71479
AB - CuI(14 TMCO) (1), involving a N3O‐macrocycle, reacts with O2 at cryogenic temperatures to yield an end‐on peroxodicopper(II) species. The N4‐analogue CuI(14‐TMC) (2) remains unreactive under similar conditions. 2 contains an average short Cu─N bond length, resulting in a dominating trans‐effect, which inhibits O2 binding. In contrast, an elongated Cu─OTMCO bond trans to the O2‐binding site in 1 allows O2‐coordination. The catalytic reduction of O2 to H2O undergoes a full 4e−/4H+ process in 1. Notably, [CuI(12‐TMC)]+ (3), involving a smaller N4‐macrocycle where the Cu(I) ion is forced to move out of the plane formed by the four nitrogen atoms, also binds O2. However, in contrast to 1, 3 mediates the catalytic 2e−/2H+ reduction of O2 to H2O2 via two ligand‐assisted protonation steps. In this case, the reduction of O2 involves the initial formation of a side‐on peroxodicopper(II) species, where the weak Cu─Operoxo bond distance resulting from the strong σ‐donation from the trans Cu─N bond presumably leads to the release of H2O2 upon protonation. The present study provides deep mechanistic insights into the transition metal‐mediated O2 reduction process and reveals how the first coordination sphere can be tuned to control the 2e−/2H+ versus 4e−/4H+ reductions of O2.
SN - 0947-6539
SN - 1521-3765
ER -