Ricerc@Sapienza

The understanding of reactive processes involving organic substrates is crucial to chemical knowledge and requires multidisciplinary efforts for its advancement. Herein, we apply a combined multivariate, statistical and theoretical analysis of coupled time-resolved X-ray absorption (XAS)/UV-Vis data to obtain detailed mechanistic information for on the C-H bond activation of 9,10-dihydroanthracene (DHA) and diphenylmethane (Ph2CH2) by the nonheme FeIV-oxo complex [N4Py·FeIV(O)]2+ (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) in CH3CN at room temperature.

In this work, we obtain detailed mechanistic and structural information on bimolecular chemical reactions occurring in solution on the second to millisecond time scales through the combination of a statistical, multivariate and theoretical analysis of time-resolved coupled X-ray Absorption Spectroscopy (XAS) and UV-Vis data. We apply this innovative method to investigate the sulfoxidation of p-cyanothioanisole and p-methoxythioanisole by the nonheme FeIV oxo complex [N4Py·FeIV(O)]2+ (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) in acetonitrile at room temperature.

In this work, we propose a method to directly determine the mechanism of the reaction between the nonheme complex FeII(tris(2-pyridylmethyl)amine) ([FeII(TPA)(CH3CN)2]2+) and peracetic acid (AcOOH) in CH3CN, working at room temperature. A multivariate analysis is applied to the time-resolved coupled energy-dispersive X-ray absorption spectroscopy (EDXAS) reaction data, from which a set of spectral and concentration profiles for the reaction key species is derived. These "pure"extracted EDXAS spectra are then quantitatively characterized by full multiple scattering (MS) calculations.