Solubilization and coordination of the HgCl2 molecule in water, methanol, acetone, and acetonitrile: an X-ray absorption investigation. Issue 30 (26th July 2022)

• Record Type: Journal Article
• Authors: Busato, Matteo; Fazio, Giuseppe; Tavani, Francesco; Pollastri, Simone; D'Angelo, Paola
• Is Part Of: Physical chemistry chemical physics. Volume 24:Issue 30(2022)
• Page Start: 18094
• Page End: 18102
• Publication Date: 2022-07-26
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d2cp02106d
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : The local structure around HgCl2 in water, methanol, acetone, and acetonitrile has been studied by means of XAS. Abstract : X-ray absorption spectroscopy (XAS) has been employed to carry out structural characterization of the local environment around mercury after the dissolution of the HgCl2 molecule. A combined EXAFS (extended X-ray absorption fine structure) and XANES (X-ray absorption near edge structure) data analysis has been performed on the Hg L3 -edge absorption spectra recorded on 0.1 M HgCl2 solutions in water, methanol (MeOH), acetone and acetonitrile. The Hg–Cl distance determined by EXAFS (2.29(2)–2.31(2) Å) is always comparable to that found in the HgCl2 crystal (2.31(2) Å), demonstrating that the HgCl2 molecule dissolves in these solvents without dissociating. A small sensitivity of EXAFS to the solvent molecules interacting with HgCl2 has been detected and indicates a high degree of configurational disorder associated with this contribution. XANES data analysis, which is less affected by the disorder, was therefore carried out for the first time on these systems to shed light into the still elusive structural arrangement of the solvent molecules around HgCl2 . The obtained results show that, in aqueous and MeOH solutions, the XANES data are compatible with three solvent molecules arranged around the HgCl2 unit to form a trigonal bipyramidal structure. The determination of the three-body Cl–Hg–Cl distribution shows a certain degree of uncertainty around the average 180° bond angle value, suggesting that the HgCl2 molecule probably vibrates in the solution around a linear configuration.