Characterization of copper complexes with derivatives of the ligand (2-aminoethyl)bis(2-pyridylmethyl)amine (uns-penp) and their reactivity towards oxygen
| Autor: | Klaus Müller-Buschbaum, Tim Brückmann, Jonathan Becker, Christian Würtele, Siegfried Schindler, Morten Weiß, Marcel T. Seuffert, Dominik Heuler |
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| Rok vydání: | 2021 |
| Předmět: |
Molecular Structure
Pyridines Ligand chemistry.chemical_element Ligands Biochemistry Copper Redox Oxygen Inorganic Chemistry chemistry.chemical_compound chemistry Ferrocene Coordination Complexes Tripodal ligand Polymer chemistry Amine gas treating Reactivity (chemistry) Cyclic voltammetry Oxidation-Reduction |
| Zdroj: | Journal of Inorganic Biochemistry. 223:111544 |
| ISSN: | 0162-0134 |
| Popis: | A series of copper(I) complexes with ligands derived from the tripodal ligand (2-aminoethyl)bis(2-pyridylmethyl)amine (uns-penp) have been structurally characterized and their redox chemistry analyzed by cyclic voltammetry. While the redox potentials of most of the complexes were similar their reactivity towards dioxygen was quite different. While the complex with a ferrocene derived ligand of uns-penp reacted in solution at low temperatures in a two-step reaction from the preliminary formed mononuclear end-on superoxido complex to a quite stable dinuclear peroxido complex it did not react with dioxygen in the solid state. Other complexes also did not react with dioxygen in the solid state while some showed a reversible formation to a green compound, indicating formation of an end-on superoxido complex that unfortunately so far could not be characterized. In contrast, copper complexes with the Me2uns-penp and Et-iProp-uns-penp formed dinuclear peroxido complexes in a solid-state reaction. While the reaction of dioxygen with the [Cu(Me2uns-penp]BPh4 was quite slow an instant reaction took place for [Cu(Et-iProp-uns-penp]BPh. Very unusual, it turned out that crystals of the copper(I) complex that could be structurally characterized still were crystalline when reacted with dioxygen. Therefore, it was possible to solve the structure of the corresponding dinuclear peroxido complex directly from the same batch of crystals. The crystalline structures of the copper(I) and copper(II) complex revealed that the reason for this is the fact, that the copper(I) complex is kind of preorganized for the uptake of dioxygen and does not really change in its overall structure when being oxidized. |
| Databáze: | OpenAIRE |
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