Second-sphere effects on H₂O₂ activation by non-heme Fe^II complexes: role of a phenol group in the [H₂O₂]-dependent accumulation of Fe^IVO vs. Fe^IIIOOH

Abstract

A new FeII complex with a phenol group attached as a second coordination sphere moiety activates H2O2 to yield FeIVO following a mechanism reminiscent of peroxidase enzymes.

Catalytic oxidation properties of an acid-resistant cross-bridged cyclen Fe(ii) complex. Influence of the rigid donor backbone and protonation on the reactivity

“…These spectra are ascribed to [(N 5 )Fe III (OMe)] 2+ in both cases, with the slight shift of the parameters being due to the protic nature of MeOH which can be hydrogen-bonded to the bound methoxo group. 48 The UV-vis signatures in MeCN and MeOH also display absorption at around 560 nm (Fig. S16 †).…”

Reaction of (N4Py)Fe with H2O2 and the relevance of its Fe(IV)=O species during and after H2O2 disproportionation

“…This paradigm mechanism has recently shown exceptions, such as in the (transient) formation of Fe(V)=O species, [8,9] in the direct dihydroxylation of alkenes with Fe(III)‐OOH species reported recently by the Nam group, [10] and in olefin epoxidation and alkene hydroxylation with a diferric peroxo intermediate reported by the Que group [11] . Additionally, control of the formation of either Fe(IV)=O or Fe(III)‐OOH species using a phenol‐bearing ligand and base was reported by the Banse group [12,13] …”

“…[11] Additionally, control of the formation of either Fe(IV) = O or Fe(III)-OOH species using a phenol-bearing ligand and base was reported by the Banse group. [12,13] Recently, we reported [14] that the complex ½FeðIIÞðN 4 PyÞðCH 3 CNÞ� 2þ (1), where N4Py is 1,1-bis(pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)methanamine), [4,5,15,16] was an effective catalyst for the disproportionation of ). Nevertheless, the formation of 1 O 2 should be excluded experimentally due to the latter's ability to initiate undesirable reactions.…”