Formation of a spirodiazaselenurane and its corresponding azaselenonium derivatives from the oxidation of 2,2 '-selenobis(benzamide). Structure, properties and glutathione peroxidase activity

The oxidation of 2,2'-selenobis(benzamide) with N-chlorosuccinimide or hydrogen peroxide afforded the corresponding stable azaselenonium chloride and hydroxide, respectively. Both structures were characterized by spectroscopic and X-ray crystallographic methods. Each contains a covalent N-Se bond, as well as a noncovalent interaction between the selenium atom and the carbonyl oxygen atom of the other amide moiety. The treatment of the azaselenonium chloride with an excess of potassium hydride in DMSO-d(6) afforded the corresponding spirodiazaselenurane species, which proved hydrolytically unstable, but was characterized by NMR spectroscopy. The azaselenonium chloride displayed significant glutathione peroxidase-like catalytic activity in an assay with benzyl thiol and either hydrogen peroxide or tert-butyl hydroperoxide.