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New mononuclear non‐heme FeII complexes derived from a well‐known pentadentate amine/pyridine ligand were synthesized. The new ligand bears an additional OH group on one pyridyl aimed at developing second sphere hydrogen bonds. Two binding modes of the ligand were observed that can be selectively obtained through the choice of the counterion: the OH group develops an intramolecular H‐bond with the 6th exogenous ligand in the classical mode, or an intermolecular one with the unbound triflate counterion in the alternative mode. The complexes were studied by cyclic voltammetry in the reductive activation of O2. The addition of an H‐bond improves the O2 activation potential with a gain of 90 mV in the classical case and 220 mV in the alternative one. The difference is ascribed to the development of stabilizing H‐bonds within the FeIII‐peroxo intermediate with the proximal O atom of peroxo (classical mode) or the distal one (alternative mode). Ultimately, the complex in the alternative mode activates O2 at −0.5 V vs SCE (500 mV gain compared to free O2). We took advantage of this significantly reduced energetic cost to carry out and achieve the electroassisted oxidation of thioanisole by O2 at −0.5 V vs SCE. [ABSTRACT FROM AUTHOR]

Three new amine/pyridine FeII complexes bearing pentadentate ligand with one, two or three electron enriched 4‐methoxy‐3,5‐dimethylpyridine were used as catalysts for the oxidation of small organic molecules by hydrogen peroxide. The distribution of products formed suggests that these ligands are not enough electron donating to promote the O−O heterolytic cleavage of the oxidant in order to generate selective FeV(O) species. Using acetic acid in the reaction mixtures results in a significant increase of the efficiency of these catalytic systems. Our investigations show that the use of AcOH leads to the protonation/dissociation of a pyridyl moiety and the formation of (N4)FeII(OAc)(OH) species. These complexes readily react with excess hydrogen peroxide to yield (N4)FeIII(OAc)(OOH) intermediates. These latter intermediates are proposed to evolve into (N4)FeIV(OAc)(O), which are more efficient than the usual (N4)FeIV(O) and (N5)FeIV(O). [ABSTRACT FROM AUTHOR]

We report two new FeIII complexes [L1FeIII(H2O)](OTf)2 and [L2FeIII(OTf)], obtained by replacing pyridines by phenolates in a known non‐heme aminopyridine iron complex. While the original, starting aminopyridine [(L52)FeII(MeCN)](PF6) complex is stable in air, the potentials of the new FeIII/II couples decrease to the point that [L2FeII] spontaneously reduces O2 to superoxide. We used it as an O2 activator in an electrochemical setup, as its presence allows to generate superoxide at a much more accessible potential (>500 mV gain). Our aim was to achieve substrate oxidation via the reductive activation of O2. While L2FeIII(OTf) proved to be a good O2 activator but a poor oxidation system, its association with another complex (TPEN)FeII(PF6)2 generates a complementary tandem couple for electro‐assisted oxidation of substrates, working at a very accessible potential: upon reduction, L2FeIII(OTf) activates O2 to superoxide and transfers it to (TPEN)FeII(PF6)2 leading in fine to the oxidation of thioanisole. [ABSTRACT FROM AUTHOR]

We report on the synthesis and characterization of three iron(III) phosphasalen complexes, [FeIII(Psalen)(X)] differing in the nature of the counter‐anion/exogenous ligand (X−=Cl−, NO3−, OTf−), as well as the neutral iron(II) analogue, [FeII(Psalen)]. Phosphasalen (Psalen) differs from salen by the presence of iminophosphorane (P=N) functions in place of the imines. All the complexes were characterized by single‐crystal X‐ray diffraction, UV/Vis, EPR, and cyclic voltammetry. The [FeII(Psalen)] complex was shown to remain tetracoordinated even in coordinating solvent but surprisingly exhibits a magnetic moment in line with a FeII high‐spin ground state. For the FeIII complexes, the higher lability of triflate anion compared to nitrate was demonstrated. As they exhibit lower reduction potentials compared to their salen analogues, these complexes were tested for the coupling of 2‐naphthol using O2 from air as oxidant. In order to shed light on this reaction, the interaction between 2‐naphthol and the FeIII(Psalen) complexes was studied by cyclic voltammetry as well as UV/Vis spectroscopy. [ABSTRACT FROM AUTHOR]

Rieske dioxygenases are metalloenzymes capable of achieving cis‐dihydroxylation of aromatics under mild conditions using O2 and a source of electrons. The intermediate responsible for this reactivity is proposed to be a cis‐FeV(O)(OH) moiety. Molecular models allow the generation of a FeIII(OOH) species with H2O2, to yield a FeV(O)(OH) species with tetradentate ligands, or {FeIV(O); OH.} pairs with pentadentate ones. We have designed a new pentadentate ligand, mtL42, bearing a labile triazole, to generate an "in‐between" situation. Two iron complexes, [(mtL42)FeCl](PF6) and [(mtL42)Fe(OTf)2]), were obtained and their reactivity towards aromatic substrates was studied in the presence of H2O2. Spectroscopic and kinetic studies reflect that triazole is bound at the FeII state, but decoordinates in the FeIII(OOH). The resulting [(mtL42)FeIII(OOH)(MeCN)]2+ then lies on a bifurcated decay pathway (end‐on homolytic vs. side‐on heterolytic) depending on the addition of aromatic substrate: in the absence of substrate, it is proposed to follow a side‐on pathway leading to a putative (N4)FeV(O)(OH), while in the presence of aromatics it switches to an end‐on homolytic pathway yielding a {(N5)FeIV(O); OH.} reactive species, through recoordination of triazole. This switch significantly impacts the reaction regioselectivity. [ABSTRACT FROM AUTHOR]

Activation of hydrogen peroxide by FeII salts (Fenton systems) leads to a myriad of oxidizing agents whose nature, FeIVO, or hydroxyl radicals and FeIII species, is dictated by the reaction conditions, in particular the pH value. Using the non heme FeII complex [FeII(L5²)(CH3CN)]2+ (1) (where L5² is the pentadentate ligand N-methyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine) we have observed the simultaneous formation of two reaction intermediates, [FeIV(O)(L5²)]2+ and [FeIII(OOH)(L5²)]2+, in its reaction with excess hydrogen peroxide in the presence of sub-stoichiometric amounts of triethylamine. Kinetic and spectroscopic monitoring of the reaction mixture and of independently prepared [FeIV(O)(L5²)]2+ in the presence of the different constituents of the reaction mixture allows drawing a mechanistic scheme. These two reactive species are formed simultaneously following two independent and competitive pathways. [FeIV(O)(L5²)]2+ is obtained via heterolytic O--O cleavage of the oxidant assisted by the base in a peroxidase-like mechanism whereas [FeIII(OOH)(L5²)]2+ is generated upon homolytic O--O cleavage of hydrogen peroxide. The relative contribution of these two pathways can be tuned by adjusting the amount of base used. [ABSTRACT FROM AUTHOR]

The reactivity and selectivity of non‐heme FeII complexes as oxidation catalysts can be substantially modified by alteration of the ligand backbone or introduction of various substituents. In comparison with the hexadentate ligand N,N,N′,N′‐tetrakis(pyridin‐2‐ylmethyl)ethane‐1,2‐diamine (TPEN), N,N′‐bis[1‐(pyridin‐2‐yl)ethyl]‐N,N′‐bis(pyridin‐2‐ylmethyl)ethane‐1,2‐diamine (2MeL62) has a methyl group on two of the four picolyl positions. FeII complexation by 2MeL62 yields two diastereomeric complexes with very similar structures, which only differ in the axial/equatorial positions occupied by the methylated pyridyl groups. In solution, these two isomers exhibit different magnetic behaviors. Whereas one isomer exhibits temperature‐dependent spin‐state conversion between the S=0 and S=2 states, the other is more reluctant towards this spin‐state equilibrium and is essentially diamagnetic at room temperature. Their catalytic properties for the oxidation of anisole by H2O2 are very different and correlate with their magnetic properties, which reflect their lability/inertness. These different properties most likely depend on the different steric constraints of the methylated pyridyl groups in the two complexes. [ABSTRACT FROM AUTHOR]

A new calix[6]arene scaffold bearing a tris-imidazole binding site at the small rim and three tetradentate aza ligands at the large rim was synthesized. The system binds three CuII ions at the large rim sites and is unable to bind a fourth one, which remains in solution. The charge repulsion between the complexes, together with the flexibility of the scaffold, disorganizes the small rim site for binding and prevents its use for host–guest studies. Although the presence of MeCN or DMF guests does not alter this state, the addition of a heptylamine guest, which further displays Brønsted basicity, restores its receptor ability by stabilizing the extra CuII ion at the tris-imidazole site with concomitant guest encapsulation and binding of an exo hydroxo ligand. This chemoselective nuclearity switch yields a tetranuclear complex in which the guest backbone is preorganized in front of three potentially reactive Cu(ii) complexes, reminiscent of polynuclear CuII enzyme active sites. [ABSTRACT FROM AUTHOR]

A heteroditopic ligand associated with a calix[6]arene scaffold bearing a tris(imidazole) coordinating site at its small rim and an amine/pyridine ligand at its large rim has been prepared, and its regioselective coordination to ZnII at the small rim and FeII in the amine/pyridine ligand has been achieved. The heterodinuclear complex obtained displays an overall cone conformation capped by the tris(imidazole)ZnII moiety and bears a non-heme FeII complex at its base. Each of the metal centers exhibits one labile position, allowing the coordination inside the cavity of a guest alkylamine at ZnII and the generation of reaction intermediates (FeIII(OOH) and FeIVO) at the large rim. A dependence between the chain length of the encapsulated alkylamine and the distribution of FeIII(OOH) intermediates and FeIII(OMe) is observed. In addition, it is shown that the generation of the FeIVO intermediate is enhanced by addition of the alkylamine guest. Hence, this supramolecular system gathers the three levels of reactivity control encountered in oxidoreductases: i) control of the FeII redox properties through its first coordination sphere, allowing us to generate high valent reactive species; ii) control of guest binding through a hydrophobic funnel that drives its alkyl chain next to the reactive iron complex, thus mimicking the binding pocket of natural systems; iii) guest-modulated reactivity of the FeII center towards oxidants. [ABSTRACT FROM AUTHOR]