Related Experiment Video
Updated: Nov 27, 2025

Structural Studies of Macromolecules in Solution using Small Angle X-Ray Scattering
Published on: November 5, 2018
Direct structural and mechanistic insights into fast bimolecular chemical reactions in solution through a coupled
Francesco Tavani1, Giorgio Capocasa, Andrea Martini
1Dipartimento di Chimica, Università di Roma "La Sapienza", P.le A. Moro 5, 00185 Roma, Italy. p.dangelo@uniroma1.it francesco.tavani@uniroma1.it.
Abstract:
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. By employing statistical and multivariate techniques we determine the number of key chemical species involved along the reaction paths and derive spectral and concentration profiles for the reaction intermediates. From the quantitative analysis of the XAS spectra we obtain accurate structural information for all reaction intermediates and provide the first structural characterization in solution of complex [N4Py·FeIII(OH)]2+. The employed strategy is promising for the spectroscopic characterization of transient species formed in redox reactions.
Related Concept Videos
Ultraviolet and Visible (UV–Vis) Spectroscopy: Overview
UV–Vis Spectroscopy of Conjugated Systems
One of the factors influencing λmax is the extent of conjugation in...
UV–Vis Spectroscopy: Molecular Electronic Transitions
UV–Vis Spectrometers
UV–Vis Spectroscopy: Woodward–Fieser Rules
UV–Vis Spectroscopy: Beer–Lambert Law

