Carbon nitride used as a reactive template to prepare mesoporous molybdenum sulfide and nitride.

Carbon nitride C3N4 has been used as a sacrificial template to prepare inorganic materials with hierarchical pore structure. C3N4 impregnated with ammonium heptamolybdate was treated in reactive gas mixtures (H2S/H2 or NH3/H2). This approach allowed mesoporous molybdenum sulfide and molybdenum nitride materials to be obtained that replicate the morphology of the C3N4 template. Advantageous catalytic properties have been demonstrated in the thiophene hydrodesulfurization (HDS) and electrochemical hydrogen evolution reaction (HER). The highest rates in both reactions were observed for partially sulfidized Mo2N solid.

Atmosphere-dependent stability and mobility of catalytic Pt single atoms and clusters on γ-Al2O3.

Atomically dispersed metals promise the ultimate catalytic efficiency, but their stabilization onto suitable supports remains challenging owing to their aggregation tendency. Focusing on the industrially-relevant Pt/γ-Al2O3 catalyst, in situ X-ray absorption spectroscopy and environmental scanning transmission electron microscopy allow us to monitor the stabilization of Pt single atoms under O2 atmosphere, as well as their aggregation into mobile reduced subnanometric clusters under H2. Density functional theory calculations reveal that oxygen from the gas phase directly contributes to metal-support adhesion, maximal for single Pt atoms, whereas hydrogen only adsorbs on Pt, and thereby leads to Pt clustering. Finally, Pt cluster mobility is shown to be activated at low temperature and high H2 pressure. Our results highlight the crucial importance of the reactive atmosphere on the stability of single-atom versus cluster catalysts.

Reshaping Dynamics of Gold Nanoparticles under H2 and O2 at Atmospheric Pressure.

Despite intensive research efforts, the nature of the active sites for O2 and H2 adsorption/dissociation by supported gold nanoparticles (NPs) is still an unresolved issue in heterogeneous catalysis. This stems from the absence of a clear picture of the structural evolution of Au NPs at near reaction conditions, i. e., at high pressures and high temperatures. We hereby report real-space observations of the equilibrium shapes of titania-supported Au NPs under O2 and H2 at atmospheric pressure using gas transmission electron microscopy. In situ TEM observations show instantaneous changes in the equilibrium shape of Au NPs during cooling under O2 from 400 °C to room temperature. In comparison, no instant change in equilibrium shape is observed under a H2 environment. To interpret these experimental observations, the equilibrium shape of Au NPs under O2, atomic oxygen, and H2 is predicted using a multiscale structure reconstruction model. Excellent agreement between TEM observations and theoretical modeling of Au NPs under O2 provides strong evidence for the molecular adsorption of oxygen on the Au NPs below 120 °C on specific Au facets, which are identified in this work. In the case of H2, theoretical modeling predicts no interaction with gold atoms that explain their high morphological stability under this gas. This work provides atomic structural information for the fundamental understanding of the O2 and H2 adsorption properties of Au NPs under real working conditions and shows a way to identify the active sites of heterogeneous nanocatalysts under reaction conditions by monitoring the structure reconstruction.

UPS and UV spectroscopies combined to position the energy levels of TiO2 anatase and rutile nanopowders.

An accurate experimental determination of electronic structures in semi-conductor nanopowders is a challenging task. We propose here to combine UPS and UV-Vis spectroscopies in order to get the full description of the electronic band alignment of powder samples, TiO2 rutile and anatase. For UPS measurements, two preparation methods, namely the dropping method and electrophoretic deposition, were used to prepare layers of titania powders on a conducting substrate, ITO or Ag. Both methods lead to comparable results, with a quantitative description of the energy levels from the valence band. Combining these results with the UV-Vis spectra of the same powders enables the determination of the absolute position of the valence band maximum and the conduction band minimum. Combined UPS-UV-Vis spectroscopy provides a better insight into the properties of a powdered material which can differ from single crystal model systems. It can also be used to predict the electronic transfer in mixed phase systems during photocatalytic processes.

Thermodynamics of faceted palladium(-gold) nanoparticles supported on rutile titania nanorods studied using transmission electron microscopy.

Many physical properties of nanoparticles (NPs) are driven by their equilibrium shape (ES). Thus, knowing the kinetic and thermodynamic parameters that affect the particle morphology is key for the rational design of NPs with targeted properties. Here, we report on the thermodynamic ES of supported monometallic palladium and bimetallic palladium-gold (Pd-Au) single-crystalline truncated nano-octahedra (TOs) studied using aberration-corrected transmission electron microscopy (TEM). Monometallic palladium and bimetallic Pd62Au38 and Pd43Au57 TOs were grown by pulsed laser deposition on rutile titania (r-TiO2) nanorods exposing mainly (110) facets. Particle structure and dimension were first obtained from aberration-corrected high resolution TEM (HRTEM) images acquired parallel to the metal-oxide interface. By fitting an extended Wulff-Kaishev rule to the HRTEM data of the truncated octahedral thermodynamic ES in the size range of 2 to 5 nm, we secondly determined the interface and excess line energies associated with the particle-oxide-vacuum triple phase junction in Pd and Pd43Au57 TOs in the epitaxial relationship Pd(-Au)(111)101‖r-TiO2(110)[1-1-1] and in Pd62Au38 TOs in the epitaxial relationship Pd62Au38(100)101‖r-TiO2(110)[1-10]. Our results show a decrease in particle adhesion to the oxide support upon alloying Pd with Au. The loss in adhesion is tentatively attributed to an increase of the lattice strain induced at the metal-oxide interface as gold atoms are added to the palladium lattice.

Understanding and controlling the structure and segregation behaviour of AuRh nanocatalysts.

Heterogeneous catalysis, which is widely used in the chemical industry, makes a great use of supported late-transition-metal nanoparticles, and bimetallic catalysts often show superior catalytic performances as compared to their single metal counterparts. In order to optimize catalyst efficiency and discover new active combinations, an atomic-level understanding and control of the catalyst structure is desirable. In this work, the structure of catalytically active AuRh bimetallic nanoparticles prepared by colloidal methods and immobilized on rutile titania nanorods was investigated using aberration-corrected scanning transmission electron microscopy. Depending on the applied post-treatment, different types of segregation behaviours were evidenced, ranging from Rh core - Au shell to Janus via Rh ball - Au cup configuration. The stability of these structures was predicted by performing density-functional-theory calculations on unsupported and titania-supported Au-Rh clusters; it can be rationalized from the lower surface and cohesion energies of Au with respect to Rh, and the preferential binding of Rh with the titania support. The bulk-immiscible AuRh/TiO2 system can serve as a model to understand similar supported nanoalloy systems and their synergistic behaviour in catalysis.

µ-Nitrido Diiron Macrocyclic Platform: Particular Structure for Particular Catalysis.

The ultimate objective of bioinspired catalysis is the development of efficient and clean chemical processes. Cytochrome P450 and soluble methane monooxygenase enzymes efficiently catalyze many challenging reactions. Extensive research has been performed to mimic their exciting chemistry, aiming to create efficient chemical catalysts for functionalization of strong C-H bonds. Two current biomimetic approaches are based on (i) mononuclear metal porphyrin-like complexes and (ii) iron and diiron non-heme complexes. However, biomimetic catalysts capable of oxidizing CH4 are still to be created. In the search for powerful oxidizing catalysts, we have recently proposed a new bioinspired strategy using N-bridged diiron phthalocyanine and porphyrin complexes. This platform is particularly suitable for stabilization of Fe(IV)Fe(IV) complexes and can be useful to generate high-valent oxidizing active species. Indeed, the possibility of charge delocalization on two iron centers, two macrocyclic ligands, and the nitrogen bridge makes possible the activation of H2O2 and peracids. The ultrahigh-valent diiron-oxo species (L)Fe(IV)-N-Fe(IV)(L(+•))═O (L = porphyrin or phthalocyanine) have been prepared at low temperatures and characterized by cryospray MS, UV-vis, EPR, and Mössbauer techniques. The highly electrophilic (L)Fe(IV)-N-Fe(IV)(L(+•))═O species exhibit remarkable reactivity. In this Account, we describe the catalytic applications of µ-nitrido diiron complexes in the oxidation of methane and benzene, in the transformation of aromatic C-F bonds under oxidative conditions, in oxidative dechlorination, and in the formation of C-C bonds. Importantly, all of these reactions can be performed under mild and clean conditions with high conversions and turnover numbers. µ-Nitrido diiron species retain their binuclear structure during catalysis and show the same mechanistic features (e.g., (18)O labeling, formation of benzene epoxide, and NIH shift in aromatic oxidation) as the enzymes operating via high-valent iron-oxo species. µ-Nitrido diiron complexes can react with perfluorinated aromatics under oxidative conditions, while the strongest oxidizing enzymes cannot. Advanced spectroscopic, labeling, and reactivity studies have confirmed the involvement of high-valent diiron-oxo species in these catalytic reactions. Computational studies have shed light on the origin of the remarkable catalytic properties, distinguishing the Fe-N-Fe scaffold from Fe-C-Fe and Fe-O-Fe analogues. X-ray absorption and emission spectroscopies assisted with DFT calculations allow deeper insight into the electronic structure of these particular complexes. Besides the novel chemistry involved, iron phthalocyanines are cheap and readily available in bulk quantities, suggesting high application potential. A variety of macrocyclic ligands can be used in combination with different transition metals to accommodate M-N-M platform and to tune their electronic and catalytic properties. The structural simplicity and flexibility of µ-nitrido dimers make them promising catalysts for many challenging reactions.

Au-Rh and Au-Pd nanocatalysts supported on rutile titania nanorods: structure and chemical stability.

Au, Rh, Pd, Au-Rh and Au-Pd nanoparticles (NPs) were synthesized by colloidal chemical reduction and immobilized on hydrothermally-prepared rutile titania nanorods. The catalysts were characterized by aberration-corrected TEM/STEM, XPS, and FTIR, and were evaluated in the hydrogenation of tetralin in the presence of H2S. Oxidizing and reducing thermal treatments were employed to remove the polyvinyl alcohol (PVA) surfactant. Reduction in H2 at 350 °C was found efficient for removing the PVA while preserving the size (ca. 3 nm), shape and bimetallic nature of the NPs. While Au-Pd NPs are alloyed at the atomic scale, Au-Rh NPs contain randomly distributed single-phase domains. Calcination-reduction of Au-Rh NPs mostly leads to separated Au and Rh NPs, while pre-reduction generates a well-defined segregated structure with Rh located at the interface between Au and TiO2 and possibly present around the NPs as a thin overlayer. Both the titania support and gold increase the resistance of Rh and Pd to oxidation. Furthermore, although detrimental to tetralin hydrogenation initial activity, gold stabilizes the NPs against surface sulfidation in the presence of 50 ppm H2S, leading to increased catalytic performances of the Au-Rh and Au-Pd systems as compared to their Rh and Pd counterparts.

Site-selective formation of an iron(iv)-oxo species at the more electron-rich iron atom of heteroleptic µ-nitrido diiron phthalocyanines.

Iron(iv)-oxo species have been identified as the active intermediates in key enzymatic processes, and their catalytic properties are strongly affected by the equatorial and axial ligands bound to the metal, but details of these effects are still unresolved. In our aim to create better and more efficient oxidants of H-atom abstraction reactions, we have investigated a unique heteroleptic diiron phthalocyanine complex. We propose a novel intramolecular approach to determine the structural features that govern the catalytic activity of iron(iv)-oxo sites. Heteroleptic µ-nitrido diiron phthalocyanine complexes having an unsubstituted phthalocyanine (Pc1) and a phthalocyanine ligand substituted with electron-withdrawing alkylsulfonyl groups (PcSO2R) were prepared and characterized. A reaction with terminal oxidants gives two isomeric iron(iv)-oxo and iron(iii)-hydroperoxo species with abundances dependent on the equatorial ligand. Cryospray ionization mass spectrometry (CSI-MS) characterized both hydroperoxo and diiron oxo species in the presence of H2O2. When m-CPBA was used as the oxidant, the formation of diiron oxo species (PcSO2R)FeNFe(Pc1)[double bond, length as m-dash]O was also evidenced. Sufficient amounts of these transient species were trapped in the quadrupole region of the mass-spectrometer and underwent a CID-MS/MS fragmentation. Analyses of fragmentation patterns indicated a preferential formation of hydroperoxo and oxo moieties at more electron-rich iron sites of both heteroleptic µ-nitrido complexes. DFT calculations show that both isomers are close in energy. However, the analysis of the iron(iii)-hydroperoxo bond strength reveals major differences for the (Pc1)FeN(PcSO2R)FeIIIOOH system as compared to (PcSO2R)FeN(Pc1)FeIIIOOH system, and, hence binding of a terminal oxidant will be preferentially on more electron-rich sides. Subsequent kinetics studies showed that these oxidants are able to even oxidize methane to formic acid efficiently.

Synthesis and characterization of µ-nitrido, µ-carbido and µ-oxo dimers of iron octapropylporphyrazine.

Three µ-X bridged diiron octapropylporphyrazine complexes having Fe(III)-O-Fe(III), Fe(+3.5)-N[double bond, length as m-dash]Fe(+3.5) and Fe(IV)[double bond, length as m-dash]C[double bond, length as m-dash]Fe(IV) structural units have been prepared and characterized by UV-vis, EPR, X-ray absorption spectroscopy and electrochemical methods. Single crystals of all the complexes were obtained from benzene-acetonitrile and their structures were determined by X-ray diffraction. In contrast to µ-oxo complex (), µ-nitrido () and µ-carbido () dimers crystallized with one benzene molecule per two binuclear complex molecules arranged cofacially to the porphyrazine planes at Fe-Cbenzene distances of 3.435-3.725 Å and 3.352-3.669 Å for and , respectively. The short distances suggest an interaction between the iron sites and the benzene π-system which is stronger in the case of the Fe(IV)[double bond, length as m-dash]C[double bond, length as m-dash]Fe(IV) unit with a higher Lewis acidity. The Fe-X-Fe angle increases in the sequence -- from 158.52° to 168.5° and 175.10°, respectively, in agreement with the Fe-X bond order. However, the lengths of the Fe-X bonds do not follow this trend: Fe-O = 1.75/1.76 Å > Fe-C = 1.67/1.67 Å > Fe-N = 1.65/1.66 Å indicating unexpectedly long Fe-C bonds. This observation can be explained by back π-donation from the µ-carbido ligand to the Fe-C antibonding orbital thus decreasing the bond order which is confirmed by DFT calculations.

X-ray absorption and emission spectroscopies of X-bridged diiron phthalocyanine complexes (FePc)2X (X = C, N, O) combined with DFT study of (FePc)2X and their high-valent diiron oxo complexes.

µ-Nitrido diiron phthalocyanine [PcFe(+3.5)NFe(+3.5)Pc](0) is an efficient catalyst, able to catalyze the oxidation of methane under near-ambient conditions. In this work, we compared the properties of structurally similar µ-carbido (1), µ-nitrido (2), and µ-oxo (3) dimers of iron phthalocyanine. The goal was to discern the structural and electronic differences between these complexes and to propose a rationale for the exceptional activity of 2. Extended X-ray fine-structure spectroscopy, high-resolution X-ray emission spectroscopy, and resonant inelastic X-ray scattering were applied to study the geometry and electronic structure of iron species in the series 1-3. The data provided by core hole spectroscopies were compared to the results of DFT calculations and found to coherently describe the structural and electronic properties of 1-3 as having equivalent iron centers with formal iron oxidation degrees of 3, 3.5, and 4 for the µ-oxo, µ-nitrido, and µ-carbido dimers, respectively. However, the bond length to the bringing atom changed in an unexpected sequence Fe-O > Fe-N < Fe-C, indicating redox non-innocence of the brigding µ-carbido ligand in 1. According to the X-ray emission spectroscopy, the µ-nitrido dimer 2 is a low-spin compound, with the highest covalency in the series 1-3. The DFT-calculated geometry and electronic structures as well as core hole spectra of hypothetical high-valent oxo complexes of 1-3 were compared, in order to explain the particular catalytic activity of 2 and to estimate the prospects of spectroscopic observation of such species. It appears that the terminal Fe═O bond is the longest in the oxo complex of 2, due to the strong trans-effect of the nitrido ligand. The corresponding LUMO of the µ-nitrido diiron oxo complex has the lowest energy among the three oxo complexes. Therefore, the oxo complex of 2 is expected to have the highest oxidative power.

Catalytic defluorination of perfluorinated aromatics under oxidative conditions using N-bridged diiron phthalocyanine.

Carbon-fluorine bonds are the strongest single bonds in organic chemistry, making activation and cleavage usually associated with organometallic and reductive approaches particularly difficult. We describe here an efficient defluorination of poly- and perfluorinated aromatics under oxidative conditions catalyzed by the µ-nitrido diiron phthalocyanine complex [(Pc)Fe(III)(µ-N)Fe(IV)(Pc)] under mild conditions (hydrogen peroxide as the oxidant, near-ambient temperatures). The reaction proceeds via the formation of a high-valent diiron phthalocyanine radical cation complex with fluoride axial ligands, [(Pc)(F)Fe(IV)(µ-N)Fe(IV)(F)(Pc(+•))], which was isolated and characterized by UV-vis, EPR, (19)F NMR, Fe K-edge EXAFS, XANES, and Kß X-ray emission spectroscopy, ESI-MS, and electrochemical techniques. A wide range of per- and polyfluorinated aromatics (21 examples), including C6F6, C6F5CF3, C6F5CN, and C6F5NO2, were defluorinated with high conversions and high turnover numbers. [(Pc)Fe(III)(µ-N)Fe(IV)(Pc)] immobilized on a carbon support showed increased catalytic activity in heterogeneous defluorination in water, providing up to 4825 C-F cleavages per catalyst molecule. The µ-nitrido diiron structure is essential for the oxidative defluorination. Intramolecular competitive reactions using C6F3Cl3 and C6F3H3 probes indicated preferential transformation of C-F bonds with respect to C-Cl and C-H bonds. On the basis of the available data, mechanistic issues of this unusual reactivity are discussed and a tentative mechanism of defluorination under oxidative conditions is proposed.

Photocatalysis with chromium-doped TiO2: bulk and surface doping.

The photocatalytic properties of TiO2 modified by chromium are usually found to depend strongly on the preparation method. To clarify this problem, two series of chromium-doped titania with a chromium content of up to 1.56 wt % have been prepared under hydrothermal conditions: the first series (Cr:TiO2) is intended to dope the bulk of TiO2, whereas the second series (Cr/TiO2) is intended to load the surface of TiO2 with Cr. The catalytic properties have been compared in the photocatalytic oxidation of formic acid. Characterization data provides evidence that in the Cr/TiO2 catalysts chromium is located on the surface of TiO2 as amorphous CrOOH clusters. In contrast, in the Cr:TiO2 series, chromium is mostly dissolved in the titania lattice, although a minor part is still present on the surface. Photocatalytic tests show that both series of chromium-doped titania demonstrate visible-light-driven photo-oxidation activity. Surface-doped Cr/TiO2 solids appear to be more efficient photocatalysts than the bulk-doped Cr:TiO2 counterparts.

Efficient epoxidation of olefins by H2O2 catalyzed by iron "helmet" phthalocyanines.

High yields of epoxides were obtained in the oxidation of a large range of olefins using 1.2-2 equiv. of H2O2 in the presence of iron helmet phthalocyanines. The involvement of high-valent iron oxo species was evidenced using cryospray mass spectrometry.

An N-bridged high-valent diiron-oxo species on a porphyrin platform that can oxidize methane.

High-valent oxo-metal complexes are involved in key biochemical processes of selective oxidation and removal of xenobiotics. The catalytic properties of cytochrome P-450 and soluble methane monooxygenase enzymes are associated with oxo species on mononuclear iron haem and diiron non-haem platforms, respectively. Bio-inspired chemical systems that can reproduce the fascinating ability of these enzymes to oxidize the strongest C-H bonds are the focus of intense scrutiny. In this context, the development of highly oxidizing diiron macrocyclic catalysts requires a structural determination of the elusive active species and elucidation of the reaction mechanism. Here we report the preparation of an Fe(IV)(µ-nitrido)Fe(IV) = O tetraphenylporphyrin cation radical species at -90 °C, characterized by ultraviolet-visible, electron paramagnetic resonance and Mössbauer spectroscopies and by electrospray ionization mass spectrometry. This species exhibits a very high activity for oxygen-atom transfer towards alkanes, including methane. These findings provide a foundation on which to develop efficient and clean oxidation processes, in particular transformations of the strongest C-H bonds.

Generation and characterization of high-valent iron oxo phthalocyanines.

The first high-valent iron oxo complex on the phthalocyanine platform has been prepared from iron tetra-tert-butyl-phthalocyanine and m-chloroperbenzoic acid and characterized by low temperature UV-vis, cryospray MS, EPR, X-ray absorption and high resolution X-ray emission methods.

High-valent diiron species generated from N-bridged diiron phthalocyanine and H(2)O(2).

N-bridged diiron tetra-tert-butylphthalocyanine activates H(2)O(2) to form anionic hydroperoxo complex [(Pc)Fe(IV)=N-Fe(III)(Pc)-OOH](-) prone to heterolytic cleavage of O-O bond with the release of OH(-) and formation of neutral diiron oxo phthalocyanine cation radical complex, PcFe(IV)=N-Fe(IV)(Pc(+)˙)=O. ESI-MS data showed stability of the Fe-N-Fe binuclear structure upon formation of this species, capable of oxidizing methane and benzene via O-atom transfer. The slow formation kinetics and the high reactivity preclude direct detection of this oxo complex by low temperature UV-vis spectroscopy. However, strong oxidizing properties and the results of EPR study support the formation of PcFe(IV)=N-Fe(IV)(Pc(+)˙)=O. Addition of H(2)O(2) at -80 °C led to the disappearance of iron EPR signal and to the appearance of the narrow signal at g = 2.001 consistent with the transient formation of PcFe(IV)=N-Fe(IV)(Pc(+)˙)=O. In the course of this study, another high valent diiron species was prepared in the solid state with 70% yield. The Mössbauer spectrum shows two quadrupole doublets with δ(1) = -0.14 mm s(-1), ΔE(Q1) = 1.57 mm s(-1) and δ(2) = -0.10 mm s(-1), ΔE(Q2) = 2.03 mm s(-1), respectively. The negative δ values are consistent with formation of Fe(iv) states. Fe K-edge EXAFS spectroscopy reveals conservation of the diiron Fe-N-Fe core. In XANES, an intense 1s → 3d pre-edge feature at 7114.4 eV suggests formation of Fe(iv) species and attaching of one oxygen atom per two Fe atoms at the 1.90 Å distance. On the basis of Mössbauer, EPR, EXAFS and XANES data this species was tentatively assigned as (Pc)Fe(IV)=N-Fe(IV)(Pc)-OH which could be formed from PcFe(IV)=N-Fe(IV)(Pc(+)˙)=O by hydrogen atom abstraction from a solvent molecule. Thus, despite unfavourable kinetics, we succeeded in the preparation of the first dirion(iv) phthalocyanine complex with oxygen ligand, generated in the (Pc)Fe(IV)=N-Fe(III)(Pc) - H(2)O(2) system capable of oxidizing methane.

From triple interpolyelectrolyte-metal complexes to polymer-metal nanocomposites.

Nanocomposite polymer materials containing metal or metal oxide particles attract growing interest due to their specific unique combination of physical and electric behavior. Stoichometric triple interpolyelectrolyte-metal complexes (TIMC) are insoluble in water and in aqueous organic media and may include high content of metal ions; concentration of ions is easy to vary in such polymeric systems. Reduction of metal ions is a common method for obtaining nanoparticles. Interpolyelectrolyte complexes reveal high permeability for polar low-molecular substances and salts. Such swelling behavior is important for the reduction of metal ions included in these solids. The properties of triple interpolyelectrolyte-metal complexes and preparation of nanocomposites from these materials using various methods of metal ion reduction are discussed in this work.

Stable N-bridged diiron (IV) phthalocyanine cation radical complexes: synthesis and properties.

Oxidation of N-bridged diiron tetra-tert-butylphthalocyanine (FePc(t)Bu)(2)N with (t)BuOOH in halogenated solvents afforded mu-nitrido diiron (IV) phthalocyanine cation radical complexes, (X)PcFe(IV)-N-Fe(IV)Pc(+) (X) (X = Cl, Br), as evidenced by UV-vis, electron paramagnetic resonance (EPR), electrospray ionization mass spectrometry (ESI-MS), Mössbauer, X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) data. Continuous introduction ESI-MS showed the initial formation of the t-butylperoxo diiron complex (t)BuOO-(FePc(t)Bu)(2)N followed by intermediate formation of a monohalogenated adduct which gave the dihalogenated complex as final stable product. Fe K-edge EXAFS analysis of (X)PcFe(IV)-N-Fe(IV)Pc(+) (X) showed bridging N atom at a distance of 1.69(1) A. The distance between two equivalent hexacoordinated in-plane iron (IV) centers is 3.39(1) A. Fe-X bond lengths are 2.33 and 2.54 A for X = Cl and Br, respectively. The use of (Cl)PcFe(IV)-N-Fe(IV)Pc(+) (Cl) for the catalytic oxidation of organic substrates has been shown for the first time.

Preparation and characterization of mu-nitrido diiron phthalocyanines with electron-withdrawing substituents: application for catalytic aromatic oxidation.

Mu-nitrido-bis [tetra-(hexyl-sulfonyl)phthalocyaninatoiron] (3a) and mu-nitrido-bis [tetra-(tert-butylsulfonyl) phthalocyaninatoiron] (3b) complexes have been prepared and fully characterized by electrospray ionization mass spectrometry, UV-Vis, FTIR, EPR, Mössbauer techniques as well as by X-ray photoelectron and Fe K-edge X-ray absorption spectroscopies. Small changes at the periphery of the phthalocyanine ligand introduce a difference in the iron oxidation state. While 3b with tert-butyl substituents is a neutral complex with a mixed-valence Fe(3.5)-N-Fe(3.5) structural unit, 3a having n-hexyl substituents is an oxidized cationic Fe(IV)-N-Fe(IV) complex. The structural parameters of N-bridged diiron phthalocyanine with a Fe(3.5)-N-Fe(3.5) unit were determined for the first time. Iron atoms in 3b are displaced out of plane by 0.24 A and the Fe-N bond distance of the linear Fe-N-Fe fragment is equal to 1.67 A. Both complexes selectively catalyze benzylic oxidation of alkyl aromatic compounds by tBuOOH. Toluene was oxidized to benzoic acid with 80% selectivity, and the total turnover number was as high as 197. p-Toluic acid was the principal product of p-xylene oxidation. In this case the turnover number achieved 587 substrate molecules per molecule of catalyst. The described catalytic system is complementary to the recently reported system based on mu-nitrido diiron tetrabutylphthalocyanine-H2O2 which effectively oxidizes the benzene ring.