Activation of C–H bonds by a nonheme iron(iv)–oxo complex: mechanistic evidence through a coupled EDXAS/UV-Vis multivariate analysis

Abstract

The understanding of reactive processes involving organic substrates is crucial to chemical knowledge and requires multidisciplinary efforts for its advancement.

Investigating the High-Temperature Water/MgCl2 Interface through Ambient Pressure Soft X-ray Absorption Spectroscopy

“…In this theoretical framework, it is possible to apply the Lambert–Beer law to retrieve the spectral and concentration profiles of the key Mg 2+ surface species contributing to the total NEXAFS measured signal . The method allows one to rationalize often complex spectroscopic XAS data sets and has been recently applied, for instance, in the mechanistic investigation of solution chemistry reactivity. ,,− In the first step, a statistical analysis based on the scree plot statistical test has been carried out, and the results are shown in Figure S3. Looking at this figure, one may observe that there is an elbow in the plot of the singular values as a function of the related principal components between the second and third component, thus indicating the presence of two components in the Mg K-edge NEXAFS data set.…”

Caught while Dissolving: Revealing the Interfacial Solvation of the Mg2+ Ions on the MgO Surface

“…The measured XAS data were then subjected to a mathematical decomposition procedure using a strategy belonging to the MCR family. This method allows the rationalization of operando spectroscopic data sets, − leading to the retrieval of the spectral and concentration profiles of the key Mg 2+ species contributing to the experimental signal. Finally, the extracted Mg K-edge XAS spectra were quantitatively analyzed through ab initio DFT NEXAFS calculations and MD simulations.…”

Two Faces of the Same Coin: Coupling X‐Ray Absorption and NMR Spectroscopies to Investigate the Exchange Reaction Between Prototypical Cu Coordination Complexes

“…For instance, recently X-ray Absorption Spectroscopy (XAS) has been coupled with UV-Vis in a stopped-flow experiment to follow transformations involving nickel, iridium and palladium complexes in solution [1,2] as well as to identify the reaction mechanisms and intermediates of a series of processes involving non-heme iron complexes, where the metal center changes its oxidation state during the reaction. [3][4][5][6] An advancement of this combined experimental approach is to couple XAS with 1 H NMR spectroscopy, a technique more informative although perhaps less straightforward if compared to UV-Vis. Indeed, the two spectroscopic methods can be considered complementary when a chemical process occurring between metal complexes and organic molecules is taken into account.…”

“…Chemical reactions predominantly occur in solution and the use of different techniques to monitor the advancement of a bimolecular chemical solution process is often a powerful tool for a satisfactory understanding of the operating reaction mechanism. For instance, recently X‐ray Absorption Spectroscopy (XAS) has been coupled with UV‐Vis in a stopped‐flow experiment to follow transformations involving nickel, iridium and palladium complexes in solution [1,2] as well as to identify the reaction mechanisms and intermediates of a series of processes involving non‐heme iron complexes, where the metal center changes its oxidation state during the reaction [3–6] . An advancement of this combined experimental approach is to couple XAS with 1 H NMR spectroscopy, a technique more informative although perhaps less straightforward if compared to UV‐Vis.…”