Selective Photo-Induced Oxidation with O 2 of a Non-Heme Iron(III) Complex to a Bis(imine-pyridyl)iron(II) Complex.

Non-heme iron(II) complexes of pentadentate N4Py ( N,N-bis(2-pyridylmethyl)- N-bis(2-pyridyl)methylamine) type ligands undergo visible light-driven oxidation to their iron(III) state in the presence of O2 without ligand degradation. Under mildly basic conditions, however, highly selective base catalyzed ligand degradation with O2 , to form a well-defined pyridyl-imine iron(II) complex and an iron(III) picolinate complex, is accelerated photochemically. Specifically, a pyridyl-CH2 moiety is lost from the ligand, yielding a potentially N4 coordinating ligand containing an imine motif. The involvement of reactive oxygen species other than O2 is excluded; instead, deprotonation at the benzylic positions to generate an amine radical is proposed as the rate determining step. The selective nature of the transformation holds implications for efforts to increase catalyst robustness through ligand design.