Bioinspired oxidation of oximes to nitric oxide with dioxygen by a nonheme iron(II) complex

The ability of two iron(II) complexes, [(Tp^Ph2)Fe^II(benzilate)] (1) and [(Tp^Ph2)(Fe^II)₂(NPP)₃] (2) (Tp^Ph2 = hydrotris(3,5-diphenylpyrazol-1-yl)borate, NPP-H = α-isonitrosopropiophenone), of a monoanionic facial N3 ligand in the O₂-dependent oxidation of oximes is reported. The mononuclear complex 1 reacts with dioxygen to decarboxylate the iron-coordinated benzilate. The oximate-bridged dinuclear complex (2), which contains a high-spin (Tp^Ph2)Fe^II unit and a low-spin iron(II)-oximate unit, activates dioxygen at the high-spin iron(II) center. Both the complexes exhibit the oxidative transformation of oximes to the corresponding carbonyl compounds with the incorporation of one oxygen atom from dioxygen. In the oxidation process, the oxime units are converted to nitric oxide (NO) or nitroxyl (HNO). The iron(II)-benzilate complex (1) reacts with oximes to afford HNO, whereas the iron(II)-oximate complex (2) generates NO. The results described here suggest that the oxidative transformation of oximes to NO/HNO follows different pathways depending upon the nature of co-ligand/reductant.Graphic abstract.