Cover Image

On the metal cooperativity in a dinuclear copper-guanidine complex for aliphatic C−H bond cleavage by dioxygen

Selective oxidation reactions of organic compounds with dioxygen using molecular copper complexes are of relevance to synthetic chemistry as well as enzymatic reactivity. In the enzyme peptidylglycine α-hydroxylating monooxygenase (PHM), the hydroxylating activity towards aliphatic substrates arises...

Full description

Saved in:
Bibliographic Details
Main Authors: Schön, Florian (Author) , Greb, Lutz (Author) , Leingang, Simone (Author) , Kaifer, Elisabeth (Author) , Himmel, Hans-Jörg (Author)
Format: Article (Journal)
Language:English
Published: July 8, 2019
In: Chemistry - a European journal
Year: 2019, Volume: 25, Issue: 48, Pages: 11257-11268
ISSN:1521-3765
DOI:10.1002/chem.201901906
Online Access:Verlag, Volltext: https://doi.org/10.1002/chem.201901906
Verlag: https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201901906
Get full text
Author Notes:Florian Schön, Florian Biebl, Lutz Greb, Simone Leingang, Benjamin Grimm‐Lebsanft, Melissa Teubner, Sören Buchenau, Elisabeth Kaifer, Michael A. Rübhausen, and Hans-Jörg Himmel
Description
Summary:Selective oxidation reactions of organic compounds with dioxygen using molecular copper complexes are of relevance to synthetic chemistry as well as enzymatic reactivity. In the enzyme peptidylglycine α-hydroxylating monooxygenase (PHM), the hydroxylating activity towards aliphatic substrates arises from the cooperative effect between two copper atoms, but the detailed mechanism has yet to be fully clarified. Herein, we report on a model complex showing hydroxylation of an aliphatic ligand initiated by dioxygen. According to DFT calculations, the proton-coupled electron-transfer (PCET) process leading to ligand hydroxylation in this complex benefits from cooperative effects between the two copper atoms. While one copper atom is responsible for dioxygen binding and activation, the other stabilizes the product of intramolecular PCET by copper-ligand charge transfer. The results of this work might pave the way for the directed utilization of cooperative effects in oxidation reactions.
Item Description:Gesehen am 12.11.2019
Physical Description:Online Resource
ISSN:1521-3765
DOI:10.1002/chem.201901906

Similar Items