Ricerc@Sapienza

The understanding of chemical reactivity relies on the development of innovative tools for its comprehension.
The present project will regard the investigation of chemical reactions by means of an innovative method that combines spectroscopic, statistical and theoretical approaches. Specifically, coupled time-resolved UV-Vis/Energy Dispersive X-ray Absorption Spectroscopy (EDXAS) data relative to bimolecular redox reactions occurring in solution, at room temperature, on the second to millisecond time scales will be analyzed using the combination of multivariate statistical and multiple scattering theoretical simulations.
The reactions under study will regard the reactivity of nonheme iron coordination complexes, an emerging class of environmentally friendly catalysts for the oxidation of organic compounds whose mechanism of action and key intermediates involved along the reactive path have not been yet fully characterized.
Firstly, the number (N) of significant species contributing to the UV-Vis/EDXAS data is established by means of statistical tests. Next, the experimental spectra will be decomposed, using a method associated to the Multivariate Curve Resolution (MCR) family, into the N spectral and N concentration profiles belonging to the reaction "pure" species. The decomposition will allow one to gain insights into the life times of all intermediates present in the reaction mixture. Further, each isolated EDXAS spectrum, associated to one of the reaction key species, will be analyzed by multiple scattering (MS) calculations. As a result, it will be possible to optimize the geometrical structure of each reaction intermediate and gain a comprehensive structural and mechanistic picture for the investigated transformations.