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

The catalytic properties of an iron complex bearing a pentadentate cross-bridged ligand backbone are reported. With HO as an oxidant, it displays moderate conversions in epoxidation and alkane hydroxylation and satisfactory ones in aromatic hydroxylation. Upon addition of an acid to the reaction medium, a significant enhancement in aromatic and alkene oxidation is observed.

Heterolytic O-O Bond Cleavage Upon Single Electron Transfer to a Nonheme Fe(III)-OOH Complex.

The one-electron reduction of the nonheme iron(III)-hydroperoxo complex, [Fe (OOH)(L )] (L =N-methyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine), carried out at -70 °C results in the release of dioxygen and in the formation of [Fe (OH)(L )] following a bimolecular process. This reaction can be performed either with cobaltocene as chemical reductant, or electrochemically. These experimental observations are consistent with the disproportionation of the hydroperoxo group in the putative Fe (OOH) intermediate generated upon reduction of the Fe (OOH) starting complex.

Fe and Fe Phosphasalen Complexes: Synthesis, Characterization, and Catalytic Application for 2-Naphthol Oxidative Coupling.

We report on the synthesis and characterization of three iron(III) phosphasalen complexes, [Fe (Psalen)(X)] differing in the nature of the counter-anion/exogenous ligand (X =Cl , NO , OTf ), as well as the neutral iron(II) analogue, [Fe (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.

Base-controlled mechanistic divergence between iron(iv)-oxo and iron(iii)-hydroperoxo in the HO activation by a nonheme iron(ii) complex.

Activation of hydrogen peroxide by Fe salts (Fenton systems) leads to a myriad of oxidizing agents whose nature, FeO, or hydroxyl radicals and Fe species, is dictated by the reaction conditions, in particular the pH value. Using the non heme Fe complex [Fe(L)(CHCN)] (1) (where L 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, [Fe(O)(L)] and [Fe(OOH)(L)], 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 [Fe(O)(L)] in the presence of the different constituents of the reaction mixture allows drawing a mechanistic scheme.

Non-Heme Fe Diastereomeric Complexes Bearing a Hexadentate Ligand: Unexpected Consequences for the Spin State and Catalytic Oxidation Properties.

The reactivity and selectivity of non-heme Fe 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 ( L ) has a methyl group on two of the four picolyl positions. Fe complexation by L yields two diastereomeric complexes with very similar structures, which only differ in the axial/equatorial positions occupied by the methylated pyridyl groups.

Selective Formation of an Fe O or an Fe OOH Intermediate From Iron(II) and H O : Controlled Heterolytic versus Homolytic Oxygen-Oxygen Bond Cleavage by the Second Coordination Sphere.

We demonstrate that the devised incorporation of an alkylamine group into the second coordination sphere of an Fe complex allows to switch its reactivity with H O from the usual formation of Fe species towards the selective generation of an Fe -oxo intermediate. The Fe -oxo species was characterized by UV/Vis absorption and Mössbauer spectroscopy. Variable-temperature kinetic analyses point towards a mechanism in which the heterolytic cleavage of the O-O bond is triggered by a proton transfer from the proximal to the distal oxygen atom in the Fe -H O complex with the assistance of the pendant amine.

Mimicking the Regulation Step of Fe-Monooxygenases: Allosteric Modulation of Fe -Oxo Formation by Guest Binding in a Dinuclear Zn -Fe Calix[6]arene-Based Funnel Complex.

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 Zn at the small rim and Fe in the amine/pyridine ligand has been achieved. The heterodinuclear complex obtained displays an overall cone conformation capped by the tris(imidazole)Zn moiety and bears a non-heme Fe complex at its base. Each of the metal centers exhibits one labile position, allowing the coordination inside the cavity of a guest alkylamine at Zn and the generation of reaction intermediates (Fe (OOH) and Fe O) at the large rim.

Self-assembled monolayer formation of a (N)Fe(ii) complex on gold electrodes: electrochemical properties and coordination chemistry on a surface.

A coordinatively unsaturated Fe complex bearing a pentadentate ligand (N,N',N'-tris(2-pyridyl-methyl)-1,2-diaminoethane) functionalized with a cyclic disulfide group has been prepared in order to graft reactive metal entities as self-assembled monolayers (SAMs) on gold electrodes. Prior to grafting, exogenous ligand exchange has been investigated by cyclic voltammetry (CV) in solution, showing that the nature of the first coordination sphere (N)Fe-X (X = Cl, OTf, MeCN, acetone) can be tuned, thanks to the control of the chemical conditions. The Fe complex has been immobilized on gold electrodes by spontaneous (passive) adsorption as well as by an electro-assisted method.

Successive light-induced two electron transfers in a Ru-Fe supramolecular assembly: from Ru-Fe(ii)-OH to Ru-Fe(iv)-oxo.

In the present work we describe the synthesis and study of a Ru-Fe chromophore-catalyst assembly designed to perform the light-induced activation of an iron bound water molecule and subsequent photo-driven oxidation of a substrate. Using a series of spectroscopic techniques, we demonstrate that excitation of the chromophore unit with 450 nm light, in the presence of a sacrificial electron acceptor, triggers a cascade of electron transfers leading to the formation of a high valent iron(iv)-oxo center from an iron(ii)-bound water molecule. The activity of this catalytic center is illustrated by the oxidation of triphenyl phosphine.

Electrochemical study of a nonheme Fe(ii) complex in the presence of dioxygen. Insights into the reductive activation of O at Fe(ii) centers.

Recent efforts to model the reactivity of iron oxygenases have led to the generation of nonheme Fe(OOH) and Fe(O) intermediates from Fe complexes and O but using different cofactors. This diversity emphasizes the rich chemistry of nonheme Fe(ii) complexes with dioxygen. We report an original mechanistic study of the reaction of [(TPEN)Fe] with O carried out by cyclic voltammetry.

Confinement of a bioinspired nonheme Fe(II) complex in 2D hexagonal mesoporous silica with metal site isolation.

A mixed amine pyridine polydentate Fe(II) complex was covalently tethered in hexagonal mesoporous silica of the MCM-41 type. Metal site isolation was generated using adsorbed tetramethylammonium cations acting as a patterned silanol protecting mask and trimethylsilylazane as a capping agent. Then, the amine/pyridine ligand bearing a tethering triethoxysilane group was either grafted to such a pretreated silica surface prior to or after complexation to Fe(II).

Iron coordination chemistry with new ligands containing triazole and pyridine moieties. Comparison of the coordination ability of the N-donors.

We report the synthesis, characterization, and solution chemistry of a series of new Fe(II) complexes based on the tetradentate ligand N-methyl-N,N'-bis(2-pyridyl-methyl)-1,2-diaminoethane or the pentadentate ones N,N',N'-tris(2-pyridyl-methyl)-1,2-diaminoethane and N,N',N'-tris(2-pyridyl-methyl)-1,3-diaminopropane, modified by propynyl or methoxyphenyltriazolyl groups on the amino functions. Six of these complexes are characterized by X-ray crystallography. In particular, two of them exhibit an hexadentate coordination environment around Fe(II) with two amino, three pyridyl, and one triazolyl groups.

Hydroxylation of aromatics with the help of a non-haem FeOOH: a mechanistic study under single-turnover and catalytic conditions.

Ferric-hydroperoxo complexes have been identified as intermediates in the catalytic cycle of biological oxidants, but their role as key oxidants is still a matter of debate. Among the numerous synthetic low-spin Fe(III)(OOH) complexes characterized to date, [(L(5)(2))Fe(OOH)](2+) is the only one that has been isolated in the solid state at low temperature, which has provided a unique opportunity for inspecting its oxidizing properties under single-turnover conditions. In this report we show that [(L(5)(2))Fe(OOH)](2+) decays in the presence of aromatic substrates, such as anisole and benzene in acetonitrile, with first-order kinetics.

Luminescent sensing and formation of mixed f-d metal ion complexes between a Eu(iii)-cyclen-phen conjugate and Cu(ii), Fe(ii), and Co(ii) in buffered aqueous solution.

The synthesis and photophysical properties of the Eu(iii) complex , based on the use of 1,10-phenanthroline (phen) as a combined sensitizing antenna and a transition metal ion coordinating ligand, is described. The long-wavelength Eu(iii) emission from this complex was found to be highly pH sensitive, giving rise to a 'off-on-off' pH profile with maximum emission occurring within the physiological pH range. This allowed for the use of as a luminescent sensor for transition metal ions, where the titration with ions such as Cu(ii), Co(ii) and Fe(ii) gave rise to the formation of mixed f-d nuclear complexes, with concomitant changes in the photophysical properties of .

Sensitized near-infrared lanthanide luminescence from Nd(III)- and Yb(III)-based cyclen-ruthenium coordination conjugates.

The development of novel mixed lanthanide-transition-metal (f-d) based supramolecular self-assemblies made from neodymium- and ytterbium-based tetraamide-functionalized cyclen complexes bearing a single 1,10-phenanthroline moiety coordinating to a RuII(bipy)2 (bipy = bipyridine) unit is described. Excitation of the Ru(II) metal-to-ligand charge-transfer band in water gave rise to long-wavelength sensitized emission from the Yb(III) or Nd(III) centers, observed in the near-infrared.

Synthesis, structural studies, theoretical calculations, and linear and nonlinear optical properties of terpyridyl lanthanide complexes: new evidence for the contribution of f electrons to the NLO activity.

The synthesis and structural, photophysical, and second-order nonlinear optical (NLO) properties of a novel lanthanide terpyridyl-like complex family LLn(NO(3))(3) (Ln = La, Gd, Dy, Yb, and Y) are reported. The isostructural character of this series in solution and in the solid state has been established on the basis of X-ray diffraction analysis in the cases of yttrium and gadolinium complexes, theoretical optimization of geometry (DFT), and NMR spectroscopy. The absorption, emission, and solvatochromic properties of the free terpyridyl-like ligand L were thoroughly investigated, and the twist intramolecular charge transfer (TICT) character of the lowest energy transition was confirmed by theoretical calculation (TDDFT and CIS).

Supramolecular self-assembly of mixed f-d metal ion conjugates.

[reaction: see text] The synthesis of the novel Eu(III) cyclen complex, Eu1, is described. In buffered pH 7.4 water, the Eu(III) emission was "switched on" upon excitation of the Terpy antenna.