A2 Refereed review article in a scientific journal
Metal Complexes of Redox Non-Innocent Ligand N,N′-Bis(3,5-di-tertbutyl-2-hydroxy-phenyl)-1,2-phenylenediamine
Authors: Lehtonen Ari
Publisher: MDPI
Publishing place: BASEL
Publication year: 2024
Journal: Molecules
Journal name in source: MOLECULES
Journal acronym: MOLECULES
Article number: 1088
Volume: 29
Issue: 5
Number of pages: 14
eISSN: 1420-3049
DOI: https://doi.org/10.3390/molecules29051088
Web address : https://doi.org/10.3390/molecules29051088
Self-archived copy’s web address: https://research.utu.fi/converis/portal/detail/Publication/387402066
Redox non-innocent ligands react with metal precursors to form complexes where the oxidation states of the ligand and thus the metal atom cannot be easily defined. A well-known example of such ligands is bis(o-aminophenol) N,N '-bis(3,5-di-tertbutyl-2-hydroxy-phenyl)-1,2-phenylenediamine, previously developed by the Wieghardt group, which has a potentially tetradentate coordination mode and four distinct protonation states, whereas its electrochemical behavior allows for five distinct oxidation states. This rich redox chemistry, as well as the ability to coordinate to various transition metals, has been utilized in the syntheses of metal complexes with M2L, ML and ML2 stoichiometries, sometimes supported with other ligands. Different oxidation states of the ligand can adopt different coordination modes. For example, in the fully oxidized form, two N donors are sp(2)-hybridized, which makes the ligand planar, whereas in the fully reduced form, the sp(3)-hybridized N donors allow the formation of more flexible chelate structures. In general, the metal can be reduced during complexation, but redox processes of the isolated complexes typically occur on the ligand. Combination of this non-innocent ligand with redox-active transition metals may lead to complexes with interesting magnetic, electrochemical, photonic and catalytic properties.
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