Inorganic Spectroscopy, Max Planck Institute for Chemical Energy Conversion, Stiftstraße 34-36, 45470, Mülheim an der Ruhr, Germany.
Department of Chemistry, Center for Metals in Biocatalysis, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN, 55455, USA.
Angew Chem Int Ed Engl. 2019 Jul 1;58(27):9114-9119. doi: 10.1002/anie.201903749. Epub 2019 May 22.
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 [Cu (μ-η :η -O )] core relative to its isomer with a cleaved O-O bond having a [Cu (μ-O) ] unit. The experimental studies are complemented by DFT calculations, which show that the unique VtC XES feature of the [Cu (μ-η :η -O )] 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-η :η -O species and highlight the potential of this method for time-resolved studies of reaction mechanisms.
价态到核（VtC）X 射线发射光谱（XES）被用于直接检测在一个包含[Cu(μ-η:η-O)]核的配合物中存在 O-O 键，而其异构体则具有断裂的 O-O 键和[Cu(μ-O)]单元。实验研究得到了 DFT 计算的补充，该计算表明[Cu(μ-η:η-O)]核的独特 VtC XES 特征对应于铜在平面内稳定的 2pπ过氧分子轨道。这些计算说明了 VtC XES 探测μ-η:η-O 物种中 O-O 键活化程度的敏感性，并突出了该方法在反应机制的时间分辨研究中的潜力。
