1. Synthesis of Thionitrites by Using Electrogenerated Cobalt(I) Salen as the Mediator Chang Ji, Department of Chemistry & Biochemistry, Texas State University – San Marcos, San Marcos, TX 78666
Thionitrites (RSNO) are synthetically useful sulfenylating/nitrosating agents and photolytic sources of thiyl radicals, as well as important nitric oxide donors for potential medical applications. Our synthetic approach utilizes the electrogenerated cobalt(I) salen as the mediator to produce thiyl radicals (RS•), which will couple with nitric oxide (NO) to form the corresponding thionitrites. We have synthesized a series of aromatic sulfenyl chlorides as the substrates, which can readily react with electrogenerated cobalt(I) salen. Cyclic voltammetric studies indicate that the reaction leads to the formation of a pentacoordinate thiylcobalt(III) salen complex. This intermediate is currently under spectroscopic examination and characterization. Our next goal is to prepare various thionitrites by the reaction of the intermediate with NO under light. A general reaction scheme is given below.