Iron(II/III) Halide Complexes Promote the Interconversion of Nitric Oxide and S-Nitrosothiols through Reversible Fe-S...

Heme and non-heme iron in biology mediate the storage/release of NO^• from S-nitrosothiols as a means to control the biological concentration of NO^•. Despite their importance in many physiological processes, the mechanisms of N-S bond formation/cleavage at Fe centers have been controversial. Herein, we report the interconversion of NO^• and S-nitrosothiols mediated by Fe^II/Fe^III chloride complexes. The reaction of 2 equiv of S-nitrosothiol (Ph₃CSNO) with [Cl₆Fe^II₂]^2- results in facile release of NO^• and formation of iron(III) halothiolate. Detailed spectroscopic studies, including in situ UV-vis, IR, and Mössbauer spectroscopy, support the interaction of the S atom with the Fe^II center. This is in contrast to the proposed mechanism of NO^• release from the well-studied "red product" κ¹-N bound S-nitrosothiol Fe^II complex, [(CN)₅Fe(κ¹-N-RSNO)]^3-. Additionally, Fe^III chloride can mediate NO^• storage through the formation of S-nitrosothiols. Treatment of iron(III) halothiolate with 2 equiv of NO^• regenerates Ph₃CSNO with the Fe^II source trapped as the S = 3/2 {FeNO}⁷ species [Cl₃FeNO]^-, which is inert toward further coordination and activation of S-nitrosothiols. Our work demonstrates how labile iron can mediate the interconversion of NO^•/thiolate and S-nitrosothiol, which has important implications toward how Nature manages the biological concentration of free NO^•.