Valence‐to‐Core X‐ray Emission Spectroscopy as a Probe of O−O Bond Activation in Cu2O2 Complexes

Valence‐to‐Core (VtC) X‐ray emission spectroscopy (XES) was used to directly detect the presence of an O−O bond in a complex comprising the [CuII2(μ‐η2:η2‐O2)]2+ core relative to its isomer with a cleaved O−O bond having a [CuIII2(μ‐O)2]2+ unit. The experimental studies are complemented by DFT calcu...

Full description

Saved in:
Bibliographic Details
Published in:Angewandte Chemie International Edition 2019-07, Vol.58 (27), p.9114-9119
Main Authors: Cutsail, George E., Gagnon, Nicole L., Spaeth, Andrew D., Tolman, William B., DeBeer, Serena
Format: Article
Language:English
Subjects:
Activation
copper
DFT
Emission spectroscopy
Mathematical analysis
Molecular orbitals
oxygen
peroxide
Reaction mechanisms
Spectroscopy
Spectrum analysis
X-ray emission spectroscopy
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Valence‐to‐Core (VtC) X‐ray emission spectroscopy (XES) was used to directly detect the presence of an O−O bond in a complex comprising the [CuII2(μ‐η2:η2‐O2)]2+ core relative to its isomer with a cleaved O−O bond having a [CuIII2(μ‐O)2]2+ unit. The experimental studies are complemented by DFT calculations, which show that the unique VtC XES feature of the [CuII2(μ‐η2:η2‐O2)]2+ core corresponds to the copper stabilized in‐plane 2p π peroxo molecular orbital. These calculations illustrate the sensitivity of VtC XES for probing the extent of O−O bond activation in μ‐η2:η2‐O2 species and highlight the potential of this method for time‐resolved studies of reaction mechanisms. Small molecule activation: Valence‐to‐core (VtC) X‐ray emission spectroscopy (XES) is shown to be a sensitive probe of the presence or absence of an O−O bond in Cu2O2 dimers possessing [CuII2(μ‐η2:η2‐O2)]2+ and [CuIII2(μ‐O)2]2+ cores, respectively.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201903749