Reduction of nitrite to nitric oxide and generation of reactive chalcogen species by mononuclear Fe(II) and Zn(II) complexes of thiolate and selenolate.

Abstract

Comparative reactivity of a series of new Zn(II) and Fe(II) compounds, [(Py2ald)M(ER)] (E = S, R = Ph: M = Zn, 1aZn; M = Fe, 1aFe; E = S, R = 2,6-Me2-C6H3: M = Zn, 1bZn; M = Fe, 1bFe; E = Se, R = Ph: M = Zn, 2Zn; M = Fe, 2Fe), and [(Py2ald)M]22+ (M = Zn, 5Zn; M = Fe, 5Fe) is presented. Compound 1aZn could react with nitrite (NO2-) to produce [(Py2ald)Zn(ONO)] (3Zn), which, upon treatment with thiols and PhSeH (proton source), could regenerate either 1aZn/5Zn and2Znrespectively, along with the production of nitric oxide (NO) where the yield of NO increases in the order tBuSH ≪ PhCH2SH < PhSH < PhSeH. In contrast to this, 1aFe, 2Fe and 5Fe could affect the direct reduction of NO2- in the absence of protons to generate NO and [{(Py2ald)(ONO)Fe}2-μ2-O] (8Fe). Moreover, 8Fe could regenerate 5Fe and 1aFe/2Fe upon treatment with 4 and 6 equiv. of PhEH (E = S/Se), respectively, along with the generation of NO. Finally, a comparative study of the mononuclear Zn(II) and Fe(II) compounds for the transfer of the coordinated thiolate/selenolate and the generation and transfer of reactive sulfur/selenium species (RES-, E = Se, S) to a series of organic substrates has been provided.