Characterization of copper complexes with derivatives of the ligand (2-aminoethyl)bis(2-pyridylmethyl)amine (uns-penp) and their reactivity towards oxygen

被引:8
|
作者
Brueckmann, Tim [1 ]
Becker, Jonathan [1 ]
Wuertele, Christian [1 ]
Seuffert, Marcel Thomas [1 ]
Heuler, Dominik [1 ]
Mueller-Buschbaum, Klaus [1 ]
Weiss, Morten [2 ]
Schindler, Siegfried [1 ]
机构
[1] Justus Liebig Univ, Inst Anorgan & Analyt Chem, Heinrich Buff Ring 17, D-35392 Giessen, Germany
[2] Univ Bayreuth, Fak Biol Chem & Geowissensch, Univ Str 30, D-95447 Bayreuth, Germany
关键词
Copper complex; Tripodal ligands; Dioxygen activation; Peroxido complex; Superoxido complex; Stopped-flow; H BOND; CRYSTAL-STRUCTURES; DIOXYGEN ADDUCTS; OXIDATION; BIS(MU-OXO)DICOPPER(III); HYDROXYLATION; SPECTROSCOPY; KINETICS; BINDING; TOLUENE;
D O I
10.1016/j.jinorgbio.2021.111544
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
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 solidstate 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.
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页数:12
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