Structural Snapshots, Trajectory and Thermodynamics of the Reversible μ-1,2-Peroxo/μ-1,1-Hydroperoxo Dicopper(II) Interconversion.

Autor: Spyra CJ; Universität Göttingen, Institut für Anorganische Chemie, Tammannstrasse 4, D-37077, Göttingen, Germany., Hiller D; Goethe-Universität, Institut für Anorganische und Analytische Chemie, Max-von-Laue-Str. 7, D-60438, Frankfurt am Main, Germany., Eisenlohr KA; Goethe-Universität, Institut für Anorganische und Analytische Chemie, Max-von-Laue-Str. 7, D-60438, Frankfurt am Main, Germany., Dechert S; Universität Göttingen, Institut für Anorganische Chemie, Tammannstrasse 4, D-37077, Göttingen, Germany., Demeshko S; Universität Göttingen, Institut für Anorganische Chemie, Tammannstrasse 4, D-37077, Göttingen, Germany., Bhattacharya D; Universität Göttingen, Institut für Anorganische Chemie, Tammannstrasse 4, D-37077, Göttingen, Germany., Lücken J; Universität Göttingen, Institut für Anorganische Chemie, Tammannstrasse 4, D-37077, Göttingen, Germany., Holthausen MC; Goethe-Universität, Institut für Anorganische und Analytische Chemie, Max-von-Laue-Str. 7, D-60438, Frankfurt am Main, Germany., Meyer F; Universität Göttingen, Institut für Anorganische Chemie, Tammannstrasse 4, D-37077, Göttingen, Germany.; Universität Göttingen, International Center for Advanced Studies of Energy Conversion (ICASEC), Tammannstrasse 6, D-37077, Göttingen, Germany.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Oct 04, pp. e202416022. Date of Electronic Publication: 2024 Oct 04.
DOI: 10.1002/anie.202416022
Abstrakt: Hydrogen bonds involving the oxygen atoms of intermediates that result from copper-mediated O 2 activation play a key role for controlling the reactivity of Cu x /O 2 active sites in metalloenzymes and synthetic model complexes. However, structural insight into H-bonding in such transient species as well as thermodynamic information about proton transfer to or from the O 2 -derived ligands is scarce. Here we present a detailed study of the reversible interconversion of a μ 1,2 -peroxodicopper(II) complex ([1] + ) and its μ 1,1 -hydroperoxo congener ([2] + ) via (de)protonation, including the isolation and structural characterization of several H-bond donor (HBD) adducts of [1] + and the determination of binding constants. For one of these adducts a temperature-dependent μ 1,2 -peroxo/μ 1,1 -hydroperoxo equilibrium associated with reversible H + -translocation is observed, its thermodynamics investigated experimentally and computationally, and effects of H-bonding on spectroscopic parameters of the Cu II 2 (μ 1,2 -O 2 ) species are revealed. DFT calculations allowed to fully map and correlate the trajectories of H + -transfer and μ 1,2 -peroxo→μ 1,1 -peroxo rearrangement. These findings enhance our understanding of two key intermediates in bioinspired Cu 2 /O 2 chemistry.
(© 2024 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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