Ligand driven heterolytic O-O bond cleavage in a non-haem phenolato-Fe(III)-OOH complex to yield a formal Fe(V)O intermediate.

ABSTRACT: Fe(V)O species can be generated by the heterolytic cleavage of the O-O bond of corresponding Fe(III)-OOH species. In haem complexes the redox non-innocence of the ligand facilitates such heterolytic cleavage, however non-haem iron complexes generally show homolytic cleavage to form an Fe(IV)O species and a hydroxyl radical. The hydroxyl radical formed is undesirable due to its non-selective reactivity. Here we show that the redox non-innocence of a phenolato ligand moiety in the complex [LFe(III)(μ-O)Fe(III)L]²⁺, where L is 2-(((di(pyridin-2-yl)methyl)(pyridin-2-ylmethyl)amino)methyl)phenolate, facilitates heterolytic O-O bond cleavage, similar in manner to that observed with haem Fe(III)-OOH species, to yield a formal Fe(V)O intermediate. Although not observed directly, the

SUBMITTER: Duijnstee DR 

PROVIDER: S-EPMC12435456 | biostudies-literature | 2025 Sep

REPOSITORIES: biostudies-literature