Insights into the Structure of Reaction Intermediates Through Coupled X-ray Absorption/UV-Vis Spectroscopy
Paper in proceeding, 2021
In this work, we propose a method for the structural characterization of chemical reaction intermediates. It allows one to analyze time-resolved coupled energy dispersive X-ray absorption spectroscopy (EDXAS) and UV-Vis reaction data through a matricial approach. Concentration profiles for the reaction key species are derived from the UV-Vis data and are used as mathematical constraints to extract their associated X-ray absorption near edge structure (XANES) spectra. The obtained XANES spectra are then quantitatively characterized by full multiple scattering (MS) calculations. We demonstrate the capabilities of this approach by applying it over a series of coupled EDXAS/UV-Vis spectra acquired in the reaction between FeII (tris(2-pyridylmethyl)amine) ([FeII(TPA)(CH3CN)2]2+ ) and H2O2. As a result, structural information for the elusive reaction key intermediate [ FeIII (TPA)(OOH)(X)]2 + is derived and it is suggested that X = CH3CN in opposition to X = H2O.
XANES
Non-heme iron complexes
Time-resolved XAS
Matricial analysis
Catalysis
Author
Francesco Tavani
Sapienza University of Rome
Andrea Martini
University of Turin
Francesco Sessa
Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry
Sapienza University of Rome
Giorgio Capocasa
Institute of Chemical Methodologies, Rome
Sapienza University of Rome
Giorgio Olivo
Sapienza University of Rome
Osvaldo Lanzalunga
Institute of Chemical Methodologies, Rome
Sapienza University of Rome
Stefano Di Stefano
Institute of Chemical Methodologies, Rome
Sapienza University of Rome
Paola D’Angelo
Sapienza University of Rome
Springer Proceedings in Physics
09308989 (ISSN) 18674941 (eISSN)
Vol. 220 141-1549783030720049 (ISBN)
Meeting of the Italian Synchrotron Radiation Society, SILS 2019
Camerino, Italy,
Camerino, Italy,
Subject Categories
Atom and Molecular Physics and Optics
Theoretical Chemistry
Organic Chemistry
DOI
10.1007/978-3-030-72005-6_11