A transition-metal-free synthetic method has been developed for the synthesis of unsymmetrical diaryl chalcogenides (S, Se, and Te) from diaryl dichalcogenides and arenes under oxidative conditions by using potassium persulfate at room temperature. Variously substituted arenes such as anisole, thioanisole, diphenyl ether, phenol, naphthol, di- and trimethoxy benzenes, xylene, mesitylene, N,N-dimethylaniline, bromine-substituted arenes, naphthalene, and diaryl dichalcogenides underwent carbon-chalcogen bond-forming reaction to give unsymmetrical diaryl chalcogenides in trifluoroacetic acid. To understand the mechanistic part of the reaction, a detailed in situ characterization of the intermediates has been carried out by (77)Se NMR spectroscopy by using diphenyl diselenide as the substrate. (77)Se NMR study suggests that electrophilic species ArE(+) is generated by the reaction of diaryl dichalcogenide with persulfate in trifluoroacetic acid. The electrophilic attack of arylchalcogenium ion on the arene may be responsible for the formation of the aryl-chalcogen bond.
Advanced tools, including atomic force microscopy (AFM), sum frequency vibrational spectroscopy (SFVS), and molecular dynamics simulations (MDS), are being used to describe interfacial water structure and to contrast the structure of water at a hydrophilic mineral surface with that at a hydrophobic mineral surface. Specifically, this contrast is revealed from interfacial water features based on the extent of H-bonding, dipole orientation, exclusion zone thickness, and residence time. Progress in our understanding of interfacial water structure and wetting phenomena is reported for different mineral classes including sulfides, oxides/hydroxides, layered silicates (phyllosilicates), and salt-type minerals, including both semi-soluble and soluble salts.
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