Reversible Proton-Coupled Reduction of an Iron Nitrosyl Porphyrin within [DBU-H]⁺-Based Protic Ionic Liquid...

The reduction of [Fe(OEP)(NO)] has been studied in the presence of aprotic room-temperature ionic liquids (RTIL) and protic (PIL) ionic liquids dissolved within a molecular solvent (MS). The cyclic voltammetric results showed the formation of RTIL nanodomains at low concentrations of the RTIL/PIL solutions. The pK_a values of the two PILs studied (i.e., trialkylammonium and [DBU-H]⁺-based ionic liquids) differed by four units in THF. While voltammetry in solutions containing all three RTILs showed similar potential shifts of the first reduction of [Fe(OEP)(NO)] to [Fe(OEP)(NO)]^- at low concentrations, significant differences were observed at higher concentrations for the ammonium PIL. The trialkylammonium cation had previously been shown to protonate the {FeNO}⁸ species at room temperature. Visible and infrared spectroelectrochemistry revealed that the [DBU-H]⁺-based PIL formed hydrogen bonds with [Fe(OEP)(NO)]^- rather than formally protonating it. Despite these differences, both PILs were able to efficiently reduce the nitrosyl species to the hydroxylamine complex, which could be further reduced to ammonia. On the voltammetric time scale and when the switching potential was positive of the Fe(II)/Fe(I) potential, the hydroxylamine complex was re-oxidized back to the NO complex via direct oxidation of the coordinated hydroxylamine at low scan rates or initial oxidation of the ferrous porphyrin at high scan rates. The results of this work show that, while [DBU-H]⁺ does not protonate electrochemically generated [Fe(OEP)(NO)]^-, it still plays an important role in efficiently reducing the nitroxyl ligand via a series of proton-coupled electron transfer steps to generate hydroxylamine and eventually ammonia. The overall reaction rates were independent of the PIL concentration, consistent with the nanodomain formation being important to the reduction process.