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通往作为酪氨酸酶模型系统的更稳定且活性更高的侧基过氧桥联(Cu(µ-η:η-O))配合物的桥梁。

The bridge towards a more stable and active side-on-peroxido (Cu(µ-η:η-O)) complex as a tyrosinase model system.

作者信息

Dalhoff Rosalie, Schmidt Regina, Steeb Lena, Rabatinova Kristina, Witte Matthias, Teeuwen Simon, Benjamaâ Salim, Hüppe Henrika, Hoffmann Alexander, Herres-Pawlis Sonja

机构信息

Institute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1a, 52074 Aachen, Germany.

出版信息

Faraday Discuss. 2023 Aug 11;244(0):134-153. doi: 10.1039/d2fd00162d.

Abstract

A novel dinucleating bis(pyrazolyl)methane ligand was developed for tyrosinase model systems. After ligand synthesis, the corresponding Cu(I) complex was synthesized and upon oxygenation, formation of a µ-η:η peroxido complex could be observed and monitored using UV/Vis-spectroscopy. Due to the high stability of this species even at room temperature, a molecular structure of the complex could be characterized single-crystal XRD. Additional to its promising stability, the peroxido complex showed catalytic tyrosinase activity which was investigated UV/Vis-spectroscopy. Products of the catalytic conversion could be isolated and characterized and the ligand could be successfully recycled after catalysis experiments. Furthermore, the peroxido complex was reduced by reductants with different reduction potentials. The characteristics of the electron transfer reactions were investigated with the help of the Marcus relation. The combination of the high stability and catalytic activity of the peroxido complex with the new dinucleating ligand, enables the shift of oxygenation reactions for selected substrates towards green chemistry, which is furthered by the efficient ligand recycling capability.

摘要

为酪氨酸酶模型系统开发了一种新型的双核双(吡唑基)甲烷配体。配体合成后,合成了相应的Cu(I)配合物,在氧化后,使用紫外可见光谱法可以观察和监测μ-η:η过氧配合物的形成。由于该物种即使在室温下也具有很高的稳定性,因此可以通过单晶X射线衍射对配合物的分子结构进行表征。除了具有令人满意的稳定性外,过氧配合物还表现出催化酪氨酸酶活性,通过紫外可见光谱法对其进行了研究。催化转化的产物可以分离和表征,并且在催化实验后配体可以成功回收。此外,过氧配合物被具有不同还原电位的还原剂还原。借助Marcus关系研究了电子转移反应的特征。过氧配合物与新型双核配体的高稳定性和催化活性相结合,能够使选定底物的氧化反应向绿色化学方向转变,而高效的配体回收能力进一步推动了这一转变。

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