Insights into the Structure of Reaction Intermediates Through Coupled X-ray Absorption/UV-Vis Spectroscopy
Paper i 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

Författare

Francesco Tavani

Sapienza, Università di Roma

Andrea Martini

Universita degli Studi di Torino

Francesco Sessa

Chalmers, Kemi och kemiteknik, Kemi och biokemi

Sapienza, Università di Roma

Giorgio Capocasa

Institute of Chemical Methodologies, Rome

Sapienza, Università di Roma

Giorgio Olivo

Sapienza, Università di Roma

Osvaldo Lanzalunga

Institute of Chemical Methodologies, Rome

Sapienza, Università di Roma

Stefano Di Stefano

Institute of Chemical Methodologies, Rome

Sapienza, Università di Roma

Paola D’Angelo

Sapienza, Università di Roma

Springer Proceedings in Physics

09308989 (ISSN) 18674941 (eISSN)

Vol. 220 141-154

Meeting of the Italian Synchrotron Radiation Society, SILS 2019
Camerino, Italy,

Ämneskategorier

Atom- och molekylfysik och optik

Teoretisk kemi

Organisk kemi

DOI

10.1007/978-3-030-72005-6_11

Mer information

Senast uppdaterat

2021-08-09